Laminate, method for manufacturing the same, and composition

Abstract

To provide a laminate having a coating film that is excellent in substrate adhesion, 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 thereof. [Solution] A laminate comprising 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 specific hydroxyl value 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 conditions: (1) further comprising inorganic fine particles B, (2) the compound A having 6 to 10 (meth)acryloyl groups comprises compound A1 having at least 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.

Description

[Technical Field]

[0001] This disclosure relates to laminates, methods for manufacturing the same, and compositions. [Background technology]

[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. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2012-229143 [Overview of the project] [Problems that the invention aims to solve]

[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. [Means for solving the problem]

[0006] The laminates, methods for manufacturing the same, and compositions relating to this disclosure are as shown in [1] to

[17] below. [1] A laminate comprising 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) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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 [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 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 [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) to 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 having 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) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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 compound (A) having 6 to 10 (meth)acryloyl groups, and satisfying at least one of the following (1) to (3): (1) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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.

[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 comprises a compound (A) having 6 to 10 (meth)acryloyl groups, 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) 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. [Effects of the Invention]

[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. [Modes for carrying out the invention]

[0008] In this specification, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described step by step in this specification, the upper limit value or lower limit value described in one numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other step-by-step descriptions. Also, in the numerical ranges described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the examples. In this specification, the (meth)acryloyl group means either one or both of the acryloyl group and the methacryloyl group, and may include these groups.

[0009] Hereinafter, embodiments of the laminate, its manufacturing method, and the composition according to the present disclosure will be described in detail. However, the present disclosure is not limited to this embodiment. Also, it can be arbitrarily modified and implemented without departing from the gist of the present disclosure.

[0010] <Laminate> The laminate according to the present disclosure (hereinafter also referred to as this laminate) includes a specific first layer and a specific second layer shown below on a substrate. Note that this laminate may have another layer on the lower side of the substrate (the side opposite to the side where the first layer is disposed), this laminate may have another layer between the substrate and the first layer, may have another layer between the first layer and the second layer, or may have another layer on the second layer. That is, this laminate only needs to have the first layer and the second layer in this order on the substrate. However, in this laminate, from the viewpoints of hardness and scratch resistance, it is preferable that the second layer is the outermost layer (the outermost surface layer). Also, in this laminate, from the viewpoint of substrate adhesion, it is preferable that the first layer is provided on the substrate surface. Furthermore, from the viewpoints of hardness, substrate adhesion, flexibility, scratch resistance, and long-term stability, it is preferable that this laminate includes a structural part composed of the substrate, the first layer, and the second layer (the outermost layer).

[0011] This laminate can be used for various applications, for example, the following applications can be cited: display panels (e.g., liquid crystal displays), touch screen panels (e.g., mobile phones, smartphones, tablet terminals, notebook PCs), electronic devices such as semiconductor elements, printed wiring boards; building applications such as buildings and houses, vehicle applications such as ships, airplanes, automobiles, industrial applications, optical applications, solar cell panels, laminates used for food packaging, etc. (e.g., glass products, films and sheets); glass products used for beakers, flasks, tableware, etc.

[0012] (Base material) The base material 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 base material can be appropriately selected according to the intended use and are not particularly limited. Examples of the material of the base material include inorganic materials (e.g., glass, quartz, sapphire), metal materials (e.g., conductive metals such as aluminum, stainless steel, titanium, gold, silver, copper, and alloys thereof), ITO (tin-doped indium oxide), IZO (indium oxide·zinc oxide), ATO (antimony-doped tin oxide), ZnO (zinc oxide), Ag (silver thin film), silver nanowires, carbon nanotubes (CNT), fullerenes, graphene, dispersion resin layers containing these, organic materials (e.g., plastic materials), paper, wood, fibrous materials, etc. The shape of the base material can be, for example, any shape such as plate-like, sheet-like, curved, etc.

[0013] The above glass is not particularly limited, but examples include silicate glass (silicate glass), soda-lime glass, potash glass. Also, the glass may 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.

[0017] The above-mentioned substrate may be a wiring board on which wiring composed 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. 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. Furthermore, the surface of the above-mentioned substrate may have characters, patterns, images, etc., printed on it.

[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. A thickness of 0.5 to 10 μm results in better adhesion, hardness, and flexibility.

[0019] [First composition] The first composition described above 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 mgKOH / g, preferably 3 to 200 mgKOH / g. If the hydroxyl value is 2 mgKOH / g or higher, adhesion to the substrate is improved. If the hydroxyl value is 300 mgKOH / g or lower, salt water resistance is improved.

[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), the side chain of the first resin (E), or 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 mgKOH / g, glass transition temperature (hereinafter referred to as Tg) 95℃, manufactured by Mitsubishi Chemical Corporation), JER4250 (Mn 9,000, hydroxyl value 180 mgKOH / g, Tg 70℃, manufactured by Mitsubishi Chemical Corporation), JER4275 (Mn 8,000, hydroxyl value 170 mgKOH / g, Tg 68℃, manufactured by Mitsubishi Chemical Corporation), and PKHA (Mn 9,000, hydroxyl value 200 mgKOH / 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 ( / g, Tg 98℃, manufactured by Gabriel Phenoxies), PKFE (Mn 16,000, Tg 98℃, manufactured by Gabriel Phenoxies), PKCP-80 (Tg 30℃, manufactured by Gabriel Phenoxies), YP-50 (Mn 14,000, Tg 84℃, manufactured by Nippon Steel Chemical & Material), YP-55U (hydroxyl value 198mgKOH / g, Tg 83℃, manufactured by Nippon Steel Chemical & Material), YP-50S (hydroxyl value 284mgKOH / g, Tg 84℃, manufactured by Nippon Steel Chemical) Examples include YP-70 (hydroxyl value 270 mgKOH / g, Tg 72℃, manufactured by Nippon Steel Chemical & Material Co., Ltd.), FX-293 (weight-average molecular weight (hereinafter, Mw) 45,000, hydroxyl value 163 mgKOH / g, Tg 158℃, manufactured by Nippon Steel Chemical & Material Co., Ltd.), FX-280S (Mw 42,000, hydroxyl value 330 mgKOH / g, Tg 158℃, manufactured by Nippon Steel Chemical & Material Co., Ltd.), and FX-310 (Mw 45,000, Tg 110℃, 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. Compounds having three or more hydroxyl groups include, but are not limited to, tolmethylolpropane, glycerin, and pentaerythritol. Polyols 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℃, manufactured by Unitika), Elitel UE3223G (Mn 20,000, hydroxyl value 5 mg KOH / g, Tg -1℃, manufactured by Unitika), Elitel UE3201 (Mn 20,000, hydroxyl value 3 mg KOH / g, Tg 65℃, manufactured by Unitika), and Elitel UE3600 (Mn 20,000, hydroxyl value 3 mg KOH / g). (Base value 4mgKOH / g, Tg 7℃, manufactured by Unitika), Elitel XA-0611 (Mn 17,000, hydroxyl value 4mgKOH / g, Tg 65℃, manufactured by Unitika), Elitel UE3200G (Mn 15,000, hydroxyl value 6mgKOH / g, Tg 65℃, manufactured by Unitika), Elitel UE3980 (Mn 8,000, hydroxyl value 17mgKOH / g, Tg 63℃, manufactured by Unitika), Elitel XP-0544 (Mn 3, 500 (Hydroxyl value 32 mg KOH / g, Tg 51℃, manufactured by Unitika), Byron 300 (Mn 23,000, Hydroxyl value 5 mg KOH / g, Tg 7℃, manufactured by Toyobo MC), Byron 630 (Mn 23,000, Hydroxyl value 5 mg KOH / g, Tg 7℃, manufactured by Toyobo MC), Byron 220 (Mn 3,000, Hydroxyl value 50 mg KOH / g, Tg 53℃, manufactured by Toyobo MC), Byron 802 (Mn 3,000, Examples include Byron GK810 (Mn 6,000, hydroxyl value 19 mg KOH / g, Tg 60℃, manufactured by Toyobo MC Co., Ltd.), Byron GK780 (Mn 11,000, hydroxyl value 11 mg KOH / g, Tg 36℃, manufactured by Toyobo MC Co., Ltd.), and Byron GK250 (Mn 10,000, hydroxyl value 11 mg KOH / g, Tg 60℃, manufactured by Toyobo MC Co., Ltd.). Furthermore, 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 with a hydroxyl value of 2 to 300 mg KOH / g.

[0029] The first resin (E) is more preferably a polyester or phenoxy resin having the specific hydroxyl value and aromatic rings 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. 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, while the hydroxyl value of the first resin (E) is 2 to 300 mg KOH / g, when using phenoxy resin, the hydroxyl value is preferably 50 to 300 mg KOH / g, and more preferably 150 to 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, in addition to particularly improved salt water resistance, flexibility, and bendability. Moreover, because phenoxy resin has a relatively high refractive index, 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. If Tg is -30°C or higher, the cohesive force is further improved. 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. If the number-average molecular weight is 1,000 or higher, 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 lower, the film strength of the protective film is increased, improving salt water resistance. 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. 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)] The isocyanate (F) can be any isocyanate group that is reactable with the hydroxyl group of the first resin (E), and is not particularly limited. The 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, the 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 the isocyanate (F) can be set appropriately within the range in which the effects of this disclosure are obtained, and is not particularly limited. Furthermore, 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 tetramethyl xylylene 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, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0039] Examples of aliphatic polyisocyanates include 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-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0040] Examples of alicyclic polyisocyanates include monocyclic alicyclic diisocyanates and cross-linked 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-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or mixtures thereof) (water Examples include diisocyanate (MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane or a mixture thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), etc.

[0042] Examples of cross-linked cyclic alicyclic diisocyanates include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(isocyanate methyl)tricyclodecane.

[0043] Examples of derivatives of these polyisocyanates include polymers of the above-mentioned isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinedione, ureitonimine, isocyanurate modified, polycarbodiimide, etc.), urethane modified (e.g., urethane modified in which a portion of the isocyanate groups in the above-mentioned isocyanate compound or polymer is modified or reacted with monool or polyol), biuret modified (e.g., biuret modified produced by the reaction of the above-mentioned isocyanate compound with water), allophanate modified (e.g., allophanate modified produced by the reaction of the above-mentioned isocyanate compound with a monool or polyol component), urea modified (e.g., urea modified produced by the reaction of the above-mentioned isocyanate compound with a diamine), oxadiazinetrione (e.g., oxadiazinetrione produced by the reaction of the above-mentioned isocyanate compound with carbon dioxide, etc.), and adduct compounds.

[0044] Among these, it is preferable to use the following as isocyanate (F): trimethylolpropane adduct of tolylene diisocyanate, isocyanurate of tolylene diisocyanate, oligomer of 4,4'-diphenylmethane diisocyanate, biuret of hexamethylene diisocyanate (HDI), isocyanurate of hexamethylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, oligomer of hexamethylene diisocyanate, uretdione of hexamethylene diisocyanate, isocyanurate of copolymer consisting of tolylene diisocyanate and hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, oligomer of isophorone diisocyanate, etc.

[0045] Examples of commercially available isocyanate (F) products 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 the 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. Furthermore, if the dissociation temperature is below 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, but are not limited to, Sumijoul 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, E402-B80B (all product names, manufactured by Asahi Kasei Chemicals Corporation), 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 Corporation).

[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] It is preferable to use 1 to 15 parts by mass of isocyanate (F) per 100 parts by mass of the first resin (E), and more preferably 2 to 13 parts by mass. That is, the mass ratio of the first resin (E) to isocyanate (F) in the first composition is preferably 100:1 to 100:15, and more preferably 100:2 to 100:13. Using 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, dimethylpolysiloxane, silicones, modified silicones such as fluorine-modified silicones, and petroleum-based resins. Antifoaming 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, and 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. Examples of leveling agents include, but are not limited to, acrylic resins, modified silicones, polyether-modified polysiloxane copolymers, dimethylpolysiloxane compounds, silicone-modified copolymers, and organic-modified polysiloxanes. Leveling agents can be used alone or in combination of two or more types.

[0055] The first composition can be further enriched with 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. Examples of aliphatic solvents include n-hexane, and examples of alicyclic solvents include cyclohexane and methylcyclohexane, but are not limited to these. Aromatic solvents include, but are not limited to, toluene, xylene, and tetralin. Solvents can be used alone 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 contains 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) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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.

[0060] [Second composition] Hereafter, a second composition that satisfies condition (1) above will also be referred to as second composition (1), a second composition that satisfies condition (2) above will also be referred to as second composition (2), and a second composition that satisfies condition (3) above will also be referred to as second composition (3). The second composition may satisfy only one of conditions (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 improved when the second composition satisfies condition (1) above. Also, the hardness of the laminate produced is improved when the second composition satisfies condition (2) above. In addition, the flexibility of the laminate produced is improved when the third composition satisfies condition (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 the components that these second compositions may contain is described in detail below.

[0061] [Compound (A)] The second composition contains compound (A). The inclusion of compound (A) provides an appropriate hardness. Compound (A) is a compound having 6 to 10 (meth)acryloyl groups (a compound with 6 to 10 functionalities). Specifically, compound (A) may include those obtained by reacting a polyisocyanate with a mono(meth)acrylate or poly(meth)acrylate having a hydroxyl group, those obtained by reacting an isocyanate group-containing urethane prepolymer, which is 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, and those obtained by reacting a hydroxyl group-containing urethane prepolymer, which is obtained by reacting a polyol and polyisocyanate under conditions of excess hydroxyl groups, with (meth)acrylates 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 60-100°C for 4-8 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 the above-mentioned aliphatic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Examples of the above-mentioned 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. In particular, from the viewpoint of suppressing yellowing when intended for optical applications, aliphatic diisocyanates are preferred among the polyisocyanates.

[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. If the number-average molecular weight of compound (A) is 500 or higher, adhesion and long-term stability (cold-heat cycle) in low-temperature and high-temperature environments are further improved. Furthermore, if the number-average molecular weight of compound (A) is 5500 or lower, 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) be 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. 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), which is a compound having 1 to 5 (meth)acryloyl groups. Including compound (C) in the second composition further improves its flexibility. Examples of compound (C) include urethane (meth)acrylate resins, epoxy (meth)acrylate resins, polyester (meth)acrylate resins, and acrylic (meth)acrylate resins, 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 urethane bonds obtained by urethane reaction between an aliphatic polyisocyanate or aromatic polyisocyanate and a (meth)acrylate having hydroxyl groups, 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 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, hydroxypivalate neopentyl glycol mono(meth)acrylate, and other dihydric alcohols. 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 acrylic (meth)acrylate resin include those obtained by polymerizing glycidyl methacrylate and, if necessary, alkyl (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, and neop 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 slitol 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 resins, epoxy (meth)acrylate resins, polyester (meth)acrylate resins, and acrylic (meth)acrylate resins, which have 11 or more (meth)acryloyl groups. Compound (D) can be used alone or in combination of two or more types.

[0083] The number average molecular weight (Mn) of compound (C) and compound (D) in the second composition is preferably 250 to 10,000, and more preferably 1,000 to 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 (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. If the acryloyl equivalents of compound (C) and compound (D) are 50 or higher, adhesion, flexibility, and long-term stability in low and high temperature environments are further improved. Furthermore, if the acryloyl equivalents of compound (C) and compound (D) are 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 using two or more 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 ingredients] The second composition may contain a photopolymerization initiator. Adding a photopolymerization initiator can further improve curability. Furthermore, the second composition may also contain a photosensitizer from the viewpoint of curability. In addition, the second composition may contain additives such as leveling agents and solvents. The leveling agents and solvents can be used in the same way as those described above in the first composition. The amounts of these additives can be set as appropriate and are not particularly limited.

[0088] Examples of the aforementioned 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, this 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 laminates> In the method for manufacturing a laminate according to this disclosure (hereinafter also referred to as the 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, the manufacturing method can be carried out, for example, by the following procedure (steps). Note that multiple steps may be carried out in parallel, or each step may be carried out sequentially.

[0093] First, the first composition is prepared. The first composition can be manufactured 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 circuit. Any known coating method can be used for coating (printing) the first composition. Preferred coating 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) step may also be performed after printing. Drying can be carried out 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 a light source with an irradiation intensity of 50-300 mW / cm². 2 By irradiating with ultraviolet light for 1 to 10 seconds, a second layer can be formed. From the above, a laminate can be obtained in which the first layer and the second layer are formed on the substrate in this order.

[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; therefore, a detailed explanation 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. [Examples]

[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 "% by mass," respectively.

[0099] <Method for calculating the number-average molecular weight of polyisocyanates> For polyisocyanates exhibiting molecular weight distribution via 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 solution. Perform the same titration, except that the Erlenmeyer flask does not contain polyisocyanate, to obtain a blank. The NCO% and number-average molecular weight can then 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 polyisocyanate-containing solution (mL) Y1: Volume (mL) of hydrochloric acid solution required for titration of a blank solution that does not contain polyisocyanate. 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: The number of NCOs contained in one molecule of polyisocyanate. • NCO%: Percentage of NCO content per molecule of polyisocyanate • Non-volatile content: Non-volatile mass % of polyisocyanate However, in this specification, the NCO% of each example polyisocyanate is based on the catalog value (the median value if a range is provided).

[0100] <Method for calculating the average molecular weight of polyols> The average molecular weight of polyols was determined using either the catalog value (the median if a range is provided) or the molecular weight calculated from the chemical formula.

[0101] <Content of polyacrylates containing hydroxyl groups> The hydroxyl group content of polyacrylate was calculated as follows: 100% if the catalog value was 97% or higher; 100% if the catalog value was less than 97% (the median if a range was provided); and 100% if the hydroxyl value was provided. The percentage 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 determined using either the catalog value (the median if a range is provided) or the molecular weight 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 consisted of four columns connected in series: "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" (all product names) manufactured by Tosoh Corporation. The mobile phase was tetrahydrofuran at 40°C, and the measurement was performed at a flow rate of 0.6 ml / min. The number-average molecular weight in polystyrene equivalent was measured and rounded to the nearest ten.

[0104] <Synthesis of compound (A)> [Synthesis Example A1] In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 596.5 parts by mass of PE-3A (trade name, manufactured by THERMO FS, 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. After raising the liquid temperature to 50°C, 168.2 parts by mass of Duranat 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 a period of 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. -1After confirming that the ) had disappeared, the temperature was lowered to room temperature (25°C). Then, urethane acrylate A1-1 (compound A1-1) (non-volatile content 100% by mass, number average molecular weight 800), a compound having six acryloyl groups, was obtained.

[0105] [Synthesis example A2] In synthesis example A1, 168.2 parts by mass of Durate 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. In FT-IR analysis, an absorption peak (2250 cm⁻¹) originating from the isocyanate group was observed. -1 The amount was confirmed to be 50% of the amount before the reaction. Then, 596.5 parts by mass of PE-3A (trade name, manufactured by THERMO FS, 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-A9] Except for changing the amounts (parts by mass) of VESTANAT IPDI and PTMG250 to those listed in Table 1, the same procedure as in Synthesis Example A3 was used to obtain urethane acrylates A1-4 to A1-9 (compounds A1-4 to A1-9), which are compounds having six acryloyl groups.

[0108] [Synthesis Example A10] In Synthesis Example A3, VESTANAT IPDI and PTMG250 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 proportions (parts by mass) of each material were changed as shown in Table 1. Except for these changes, the synthesis was carried out in the same manner 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] In Synthesis Example A3, PTMG250 and PE-3A 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 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. Apart from 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] [Table 1]

[0113] <Synthesis of compound (C)> [Synthesis example C1] In Synthesis Example A1, Duranat 50M-HDI and PE-3A were replaced with Duranat 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] Furthermore, except for the addition of Purchase DPPA and the changes in the proportions (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] In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 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 Duranat 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 part 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. -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 FS, 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. -1After confirming that the ) had disappeared, the temperature was lowered to room temperature, and urethane acrylate D-2 (compound D-2) (non-volatile content 90.7% by mass, number average molecular weight 9000), a compound having 15 acryloyl groups in the non-volatile content, was obtained.

[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. After raising the liquid temperature to 50°C, 545.7 parts by mass of Duranat 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 a period of 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] [Table 2]

[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] [Table 3]

[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℃, 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 Durate 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 solution (first composition). Next, the first composition was coated onto Eagle XG alkali-free glass (Corning, 0.7 mm thick) 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. 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 (product name, manufactured by MIWON, a mixture of 95.3% dipentaerythritol hexaacrylate (DPE-6A), a compound having 6 acryloyl groups, and 4.7% dipentaerythritol pentaerythritol (DPE-5A), a compound having 5 acryloyl groups) 100 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) • 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, • 139.3 parts by mass of methyl ethyl ketone. The second composition described above was applied to the anchor layer (first layer) using a bar coater so that the film thickness after drying was 6.0 μm. Then, a high-pressure mercury lamp was used to heat the surface at 400 mJ / cm². 2 Two types of laminates (a laminate with a glass substrate and a laminate with a PET film substrate) having a first and second layer were fabricated by irradiating them with ultraviolet light, and the evaluations described below were performed. The evaluation results are shown in Table 4. Note that the amount (parts by mass) of each component in Table 4 refers to the amount (content) of non-volatile components.

[0122] <Evaluation Criteria> (Adhesion) Tape adhesion tests were conducted using laminates fabricated on glass. The tape adhesion tests were performed in accordance with JIS K5600. A utility knife was used to create 100 grid squares (10x10) at 1mm intervals, reaching a depth that did not cut through the substrate. Cellophane tape (25mm wide, manufactured by Nichiban) was then applied to the surface of the coating, and the tape was rapidly peeled off by hand. The state of the remaining grid squares was then observed. The results were evaluated based on the following evaluation criteria. • Evaluation criteria A: No peeling (0 peeled cells) (Excellent condition). B: Slight chipping at the edge of the squares, or peeling of 1 to 5 squares is observed (good). C: Peeling is observed in 6 or more sections (not practical).

[0123] (Pencil hardness) Using laminates fabricated on glass, scratch tests were conducted according to JIS K5600-5-4, by applying pencils of various hardnesses at a 45° angle to the surface of the hard coat layer (second layer) of the laminate and applying a load. The results were evaluated based on the following evaluation criteria. • Evaluation criteria AA: 7H or more (very good). A: 5~6H (good). B: 3-4H (No practical problems). C: 2H or less (not practical).

[0124] (Scratch resistance) Using the laminate prepared on glass, the scratch resistance was evaluated with a "Gakushin-type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. A friction pad (surface area 4 cm 2 ) with a 1000 g load attached was fitted with steel wool #0000, and the surface (2 cm × 15 cm) of the hard coat layer (second layer) was reciprocated 10 times. Then, the number of scratches on the surface of the hard coat layer was counted and evaluated according to the following criteria. The fewer the number of scratches, the better, and if it is 9 or less, it can be used without 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 the laminate prepared on a PET film, a bending test was carried out with a bending tester (a flat body unloaded U-shaped expansion and contraction tester manufactured by Yuasa System Devices Co., Ltd.) with the hard coat layer (second layer) set on the device so that it was on the lower side, and bending was performed 10,000 times at a speed of 60 times per minute with a diameter of 3 mm and a width of 60 mm. Then, the measurement results were evaluated based on the following evaluation criteria. ·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 in low-temperature and high-temperature environments) Using the laminate prepared on glass, a long-term stability (thermal cycle) test was carried out with a "Small Thermal Shock Device TSE-11-A (trade name)" manufactured by ESPEC Corporation. Specifically, the surface of the coating film after 200 cycles at a low temperature of -40°C, a high temperature of 100°C, and an exposure time of 40 minutes each was visually observed and evaluated based on the following evaluation criteria. • Evaluation criteria A: No cracks (very good) B: One crack (no practical problem) C: Two or more cracks (unusable)

[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 to 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 synthesis example described above. 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] [Table 4]

[0129] [Example 12] 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 a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials. 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)) • Compound A2-1 (non-volatile content 91.9%) 108.8 parts by mass (non-volatile content: 100 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) • 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, • 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 and 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 used in the second composition, corresponding to compounds (A1) and (C), was changed to 50 parts by mass, and 50 parts by mass of compound A1-4 were also 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 in the second composition, corresponding to compounds (A1) and (C), 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 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.

[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 to 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 two layers 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 synthesis example described above, 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. • Compound A2-1, which corresponds to compound (A2) and was synthesized in the above-described synthesis example, 60 parts by mass. • 40 parts by mass of 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), 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 129.2 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.

[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. • Compound A2-3, which corresponds to compound (A2) and was synthesized in the above-described synthesis example, 50 parts by mass. • Compound (C) is equivalent to 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). 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. • Compound A2-3, which corresponds to compound (A2) and was synthesized in the above-described synthesis example, 50 parts by mass. • 20 parts by mass of Arronix M315, corresponding to compound (C). Aside from the above, two types of laminates having a first layer and a second layer were fabricated and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0138] [Table 5]

[0139] [Example 24] 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 a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials. 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)) • Compound A1-1 (non-volatile content 100.0%) 90 parts by mass, (Compound (C)) • 10 parts by mass of the above compound C-1 (non-volatile content 100.0%) (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, • 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 proportions (non-volatile content), as shown in Table 6, two types of laminates having a first layer and two types having a second layer were prepared in the same manner as in Example 24 and evaluated. The evaluation results are shown in Table 6.

[0141] [Table 6]

[0142] [Example 34] 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 a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials. 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 the 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) • 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) • DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator) 5.0 parts by mass, • 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 proportions (non-volatile content), as shown in Table 7, two types of laminates having a first layer and two types having a second layer were prepared in the same manner as in Example 34 and evaluated. The evaluation results are shown in Table 7. In addition, the amount of methyl ethyl ketone in Example 34 (120.6 parts by mass) 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] [Table 7]

[0145] [Example 41] 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 a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials. 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)) • MEK-AC-2140Z (product name, manufactured by Nissan Chemical Corporation, silica nanoparticles, MEK (methyl ethyl ketone, non-volatile content 46.0%) dispersion, 10.87 parts by mass (non-volatile content: 5 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, • 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 two types having 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 to 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 and evaluated 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. The evaluation results are shown in Table 8. (Compound (A1)) • 90 parts by mass of the above compound A1-4 (non-volatile content 100.0%) (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) • DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator) 5.0 parts by mass, • 124.4 parts by mass of methyl ethyl ketone.

[0148] [Table 8]

[0149] [Comparative Example 1] 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 a hard coat liquid (second composition, 45% non-volatile content) was used, which was prepared by mixing and dissolving the following materials. 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) • 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, • 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. Furthermore, 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 and evaluated 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. The evaluation results are shown in Table 9. (Compound (C)) • Arronix M450 (product 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) 100 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, • 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 (100 parts by mass of non-volatile content) of MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation), a silica nanoparticle, MEK (methyl ethyl ketone, 46.0% non-volatile content) dispersion, was 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 two types having a second layer were prepared and evaluated in the same manner as in Comparative Examples 8 and 9. 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 and evaluated 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. The evaluation results are shown in Table 9. (Compound (C)) • Arronix M450 (product name, manufactured by Toagosei Co., Ltd.), 20 parts by mass of a mixture containing 90% by mass of pentaerythritol tetraacrylate (PE-4A) with an average molecular weight of 352.3 and 10% by mass of pentaerythritol triacrylate (PE-3A) with an average molecular weight of 298.3. (Compound (D)) • Compound D-2 (non-volatile content 90.7%) 88 parts by mass (non-volatile content 80 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) • DAIDO UV-CURE #174 (product name, manufactured by Daido Chemical Industries, Ltd., photopolymerization initiator) 5.0 parts by mass, • 112.4 parts by mass of methyl ethyl ketone.

[0155] [Comparative Example 13] In the second composition of Comparative Example 12, 217.4 parts by mass (100 parts by mass of non-volatile content) of MEK-AC-2140Z (trade name, manufactured by Nissan Chemical Corporation), which is an inorganic fine particle (B), was added as a dispersion of MEK (methyl ethyl ketone, 46.0% non-volatile content) silica nanoparticles. 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] [Table 9]

[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 isophorone. Next, 8.3 parts by mass (5 parts by mass of non-volatile content) of Durate 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 anchoring solution (first composition). Next, the first composition was coated onto Eagle XG alkali-free glass (Corning, 0.7 mm thick) 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. 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 6 acryloyl groups, and 4.7% dipentaerythritol pentaerythritol (DPE-5A), a compound having 5 acryloyl groups) 47.2 parts by mass, (Compound (A2)) ·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, • 134.5 parts by mass of methyl ethyl ketone. The second composition described above was applied to the anchor layer (first layer) using a bar coater to achieve a film thickness of 6.0 μm after drying. Then, a high-pressure mercury lamp was used to heat the surface at 400 mJ / cm². 2 Two types of laminates (a laminate with a glass substrate and a laminate with a PET film substrate) having a first layer and a second layer were fabricated by irradiating them with ultraviolet light, 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 to 58, the first resin (E) was changed to the following. The evaluation results are shown in Table 10. • Elitel 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) • Elitel 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) • Elitel 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) • Elitel 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) • Elitel 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] [Table 10]

[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 to 68, the isocyanate (F) was changed to the following, respectively. 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) Durate 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℃, non-volatile content 100%) (Isocyanate) • Sumidure N3300 (Trade name, manufactured by Sumitomo Covestro Urethane Co., Ltd., HDI, 100% non-volatile content) • Desmodure IL 1351 BA (product name, manufactured by Sumitomo Covestro Urethane Co., Ltd., TDI, non-volatile content 51%)

[0161] [Table 11]

[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 to 16, the first resin (E) was changed to the following, respectively. 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 (product 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 (Product name, manufactured by Eastman Chemical Company, hydroxyl value 53 mg KOH / g, number average molecular weight Mn 30000, non-volatile content 100%, cellulose acetate butyrate resin) • CA-398-3 (Product name, manufactured by Eastman Chemical Company, hydroxyl value 116 mg KOH / g, number average molecular weight Mn 50000, 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 anchoring liquid (first composition), and 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 anchoring liquid (first composition) was not used and the first layer was not prepared, and only the second layer was prepared on the substrate, and then evaluated. The evaluation results are shown in Table 12.

[0165] [Table 12]

[0166] [Examples 69-76] As shown in Table 13, two types of laminates were prepared and evaluated in the same manner as in Example 16, except that the thickness of the first and second layers (film thickness after curing) was changed. The evaluation results are shown in Table 13.

[0167] [Table 13]

[0168] From the above, it can be seen that the present laminate having the specific first layer and the specific second layer on the substrate is excellent in substrate adhesion, hardness, flexibility, scratch resistance, and long-term stability in low-temperature and high-temperature environments.

[0169] Note that the present disclosure is not limited to the above-described embodiments and can be appropriately modified without departing from the gist. Also, the present disclosure may be implemented by appropriately combining the above-described embodiments and examples thereof.

Industrial Applicability

[0170] The laminate, its manufacturing method, and the composition according to the present disclosure can be used in various applications such as electronic devices such as display panels, touch screen panels, semiconductor elements, and printed wiring boards; building applications such as buildings and houses, vehicle applications such as ships, aircraft, and automobiles, industrial applications, optical applications, solar cell panels, laminates used in food packaging, etc.; glass products used in beakers, flasks, tableware, etc.

Claims

1. On the 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), A second layer which is a cured product of a second composition comprising compound (A) having 6 to 10 (meth)acryloyl groups and satisfying at least one of the following (1) to (3), Laminates equipped with: (1) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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, 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 second composition contains a compound (A) having 6 to 10 (meth)acryloyl groups, and 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. The laminate according to claim 1, wherein the mass ratio of compound (A), compound (C), and compound (D) is 98:2 to 70:

30.

5. The second composition contains inorganic fine particles (B), The laminate according to claim 1, wherein the inorganic fine particles (B) include silica (B1) or alumina (B2).

6. The second composition contains inorganic fine particles (B), The laminate according to claim 1, wherein 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 claim 1, wherein the glass transition temperature of the first resin (E) is -30 to 170°C.

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

9. The laminate according to claim 1, 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 claim 1, 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) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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 compound (A) having 6 to 10 (meth)acryloyl groups, and satisfying at least one of the following (1) to (3): (1) Furthermore, including inorganic fine particles (B), (2) Compound (A) having 6 to 10 (meth)acryloyl groups comprises compound (A1) having at least 6 to 8 (meth)acryloyl groups and 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.

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, 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 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. The composition according to claim 12, wherein the mass ratio of compound (A), compound (C), and compound (D) is 98:2 to 70:

30.

16. The composition contains inorganic fine particles (B), The composition according to claim 12, wherein the inorganic fine particles (B) include silica (B1) or alumina (B2).

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

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