Laminated film, structure, and method for producing structure

Abstract

To provide a laminated film having realized excellent adhesivity to a building material while controlling adhesivity to a substrate, a structure, and a preparation method of a structure.SOLUTION: Provided is a laminated film for coating an inorganic material surface, comprising a substrate and a curable resin layer laminated on the substrate, where the curable resin layer comprises the following components: (A) a binder polymer, (B) a compound having an ethylenic unsaturated double bond, and (C) a polymerization initiator, A weight average value Tgtotal of a glass transition temperature Tg of the (A) binder polymer is 55°C to 120°C. The curable resin composition contains a reactive oligomer having 1 or more unsaturated groups in an amount of 0 to less than 10 pts.mass based on 100 pts.mass of the (A) component. A thickness of the curable resin layer is 20 μm or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated film, a structure, and a method for producing the structure. [Background technology]

[0002] Typically, interior and exterior materials for buildings such as houses include concrete, wood, and resin. For example, the surface of lightweight aerated concrete (ALC) is coated with a coating to protect the base material, prevent performance degradation due to water intrusion, and prevent carbonation due to carbon dioxide intrusion. Lightweight aerated concrete, in particular, is typically manufactured into panels at a manufacturing plant and then transported to a construction site. These panels are then laid on a framework to form a building, after which the exterior wall surfaces are painted. Such lightweight aerated concrete panels have various problems, including their foam structure making them prone to chipping and other damage during transportation; their foam structure also makes them prone to dust shed from fine cracks and chips during transportation and installation; and the unevenness of their surface due to their foam structure makes it difficult to achieve a smooth surface.

[0003] When forming a coating on the surface of such concrete, especially lightweight aerated concrete panels, painting techniques are often used. Generally, multiple coats of paint are applied, such as a primer, intermediate coat, and top coat. These paints are often dispersed or diluted in liquid, and the process of applying these paints to the surface of concrete, especially lightweight aerated concrete panels, and then allowing the liquid components to dry is often repeated.

[0004] This method requires a considerable amount of time for the coating material to dry, and if multiple coats are applied, the coating process takes a considerable amount of time, resulting in poor productivity and workability.Further improvement is also required in terms of the protection of the concrete surface.

[0005] Therefore, with the aim of forming a coating film on the surface of concrete that is excellent in productivity and workability and also excellent in protecting the concrete surface, a method has been proposed in which a laminated film consisting of a layer of a curable resin composition and a support film is attached to the surface of concrete, and the curable resin composition layer is cured to form a coating film (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6324220 [Patent Document 2] Patent No. 6489931 Summary of the Invention [Problem to be solved by the invention]

[0007] However, with such laminated films, it is important to control the adhesion to concrete. While high adhesion between the substrate and resin layer is desirable, if the adhesion is too high, the resin layer will be easily carried away by the substrate when peeling the substrate from the resin layer after the laminated film is applied to a concrete panel, leading to a deterioration in appearance. Furthermore, edge fuses are likely to occur when the laminated film is stored in a roll, making long-term storage difficult.

[0008] On the other hand, since the surface of a concrete panel is uneven, if the adhesion to the concrete panel is too high, the resin layer will conform to the uneven surface, causing the unevenness to stand out on the surface of the resin layer and degrading the appearance.

[0009] Until now, no studies have been conducted on films that can "control adhesion to the substrate" while also achieving "excellent adhesion to inorganic materials."

[0010] The present invention has been proposed in view of the above-described conventional situation, and an object of the present invention is to provide a laminated film, a structure, and a method for producing a structure that realizes excellent adhesion to building materials while controlling adhesion to a substrate. [Means for solving the problem]

[0011] [1] A substrate and a curable resin layer laminated on the substrate, The curable resin layer comprises the following components (A) to (C): (A) a binder polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a polymerization initiator, A laminated film for covering the surface of a building material, comprising a curable resin composition comprising: The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) total is 55°C or more and 120°C or less, The curable resin composition contains a reactive oligomer having one or more unsaturated groups in an amount of 0 parts by mass or more and less than 10 parts by mass, based on 100 parts by mass of component (A), and the thickness of the curable resin layer is 20 μm or more. [2] The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) total The laminated film according to [1], wherein the temperature is 55°C or higher and 100°C or lower. [3] The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) total The laminated film according to [1], wherein the temperature is 55°C or higher and 85°C or lower. [4] The laminate film according to any one of [1] to [3], wherein the curable resin composition contains a reactive oligomer having one or more unsaturated groups below the detection limit based on 100 parts by mass of the component (A). [5] The laminated film according to any one of [1] to [4], wherein the reactive oligomer having one or more unsaturated groups is a total of a urethane (meth)acrylate compound, an epoxy (meth)acrylate compound, and a polyester (meth)acrylate compound. [6] The laminated film according to any one of [1] to [5], wherein the thickness of the curable resin layer is 50 μm or more. [7] The laminated film according to any one of [1] to [6], wherein the adhesiveness to the substrate is 3 gf or more and less than 30 gf in a tackiness test when the substrate is polyethylene terephthalate. [8] The laminated film according to any one of [1] to [6], wherein the building material is a base material containing an inorganic material as a main component. [9] The laminate film according to any one of [1] to [6], wherein in a cross-cut test, the ratio of the peeled area of ​​the curable resin layer to the base material containing the inorganic material as a main component is less than 20%.

[10] The laminated film according to any one of [1] to [6], wherein the press flow value for a base material containing the inorganic material as a main component is 500 to 2000 μm in a press flow test.

[11] In the curable resin layer, The content of the component (A) is 20% by mass to 80% by mass, The content of the component (B) is 20% by mass to 60% by mass, The content of the component (C) is 3.0% by mass to 10% by mass. The laminated film according to any one of [1] to

[10] .

[12] The laminated film according to any one of [1] to

[11] , wherein the thickness of the curable resin layer is 80 to 500 μm.

[13] The laminated film according to any one of [1] to

[12] , wherein the component (A) contains a (meth)acrylic resin and contains benzyl (meth)acrylate as a monomer component.

[14] The laminated film according to any one of [1] to

[13] , wherein the component (B) contains a bifunctional monomer and a tetrafunctional monomer.

[15] The laminated film according to any one of [1] to

[14] , further comprising a cover film disposed on the side of the curable resin layer opposite to the side on which the substrate is disposed.

[16] The laminated film according to any one of [1] to

[15] , wherein the curable resin composition further contains a dye.

[17] the curable resin composition contains an organic solvent, The laminate film according to any one of [1] to

[16] , wherein the amount of the organic solvent remaining in the curable resin layer is 0.5 parts by mass to 5 parts by mass based on 100 parts by mass of the curable resin layer.

[18] The laminated film according to any one of [1] to

[17] , wherein the amount of the polymerization initiator (C) is 2.5 parts by mass to 15 parts by mass based on the total amount of the components (A) to (C).

[19] The laminated film according to any one of [1] to

[18] , wherein the (C) polymerization initiator is a photopolymerization initiator.

[20] The laminated film according to

[19] , containing an imidazole compound as the photopolymerization initiator. [twenty one] A structure comprising a base building material mainly composed of an inorganic material and a laminate film according to any one of [1] to

[20] laminated on the building material. [twenty two] The structure according to

[21] , wherein the building material includes a sealant layer (resin layer) on the surface of the laminated film side. [twenty three] The structure according to

[21] or

[22] , wherein the building material is a base material whose main component is an inorganic material. [twenty four] a step of laminating the curable resin layer side of the laminated film according to any one of [1] to

[20] on a base material containing an inorganic material as a main component; a step of curing the curable resin layer with light or heat to form a cured resin film; A method for fabricating a structure, comprising: [twenty five] The method for producing a structure according to

[24] , wherein the building material is a base material whose main component is an inorganic material. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a laminated film, a structure, and a method for producing a structure that realizes excellent adhesion to building materials while controlling adhesion to a substrate. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a cross-sectional view showing one example of the configuration of a laminated film of the present invention. [Figure 2] 1 is a cross-sectional view showing an example of the structure of the present invention. [Figure 3] FIG. 10 is a cross-sectional view illustrating how a laminated film is attached to the surface of a concrete panel. DETAILED DESCRIPTION OF THE INVENTION

[0014] An exemplary embodiment of the present invention (hereinafter abbreviated as "the present embodiment") will be described in detail below. The present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist of the present invention. In this specification, the upper and lower limits of each numerical range can be combined arbitrarily. In this specification, numerical ranges expressed using "to" include the upper and lower limit values.

[0015] Also, in this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.

[0016] [Laminated film] FIG. 1 is a cross-sectional view showing an example of the structure of the laminated film of the present invention. The laminated film 1 of the present invention has a substrate 10 and a curable resin layer 11 laminated on the substrate 10, The curable resin layer 11 comprises the following components (A) to (C): (A) a binder polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a polymerization initiator, A laminated film for covering the surface of a building material, comprising a curable resin composition comprising: (A) Weight average value of glass transition temperature Tg of binder polymer total is 55℃ to 120℃, The curable resin composition contains, based on 100 parts by mass of the component (A), 0 parts by mass or more and less than 10 parts by mass of a reactive oligomer having one or more unsaturated groups, The thickness of the curable resin layer 11 is 20 μm or more.

[0017] This laminated film 1 is used for surface coating of building materials, such as concrete, panels made of lightweight aerated concrete (ALC), extruded cement boards, gypsum boards, sandwich panels, ceramic sanding, metal siding, and resin siding.

[0018] In the following explanation, we will mainly use as an example a case where the building material is an ALC panel as the base material 110 whose main component is an inorganic material, but the type of building material to which the laminated film 1 of the present invention is applied and the form of the base material 110 are not particularly limited.

[0019] The laminated film 1 of the present invention can achieve excellent adhesion to building materials, for example, the base material 110 containing inorganic materials as the main component, while controlling the adhesion to the substrate 10.

[0020] Furthermore, the laminated film 1 may have a cover film 12 laminated on the surface of the curable resin layer 11 opposite to the substrate 10, as required.

[0021] <Base material> The substrate 10 serves as a support when the curable resin layer 11 is formed and when the laminate film 1 is attached to a building material, for example, a base material 110 mainly composed of an inorganic material, and for example, by applying a curable resin composition to the substrate 10 and drying it, the curable resin composition is retained as the curable resin layer 11. Furthermore, the substrate 10 also serves as a protective film to prevent scratches, dirt, and chips from occurring during storage, transportation, or installation of the laminate film 1 on an ALC panel, and as a patch when the laminate film 1 is thermocompression bonded to the ALC panel.

[0022] The substrate 10 is preferably transparent and transmits light, such as sunlight. Examples of such substrates 10 include films made of polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, vinyl chloride copolymers, polyvinylidene chloride, vinylidene chloride copolymers, polymethyl methacrylate copolymers, polystyrene, polyacrylonitrile, styrene copolymers, polyamides, and cellulose derivatives. These films may also be stretched as needed. Among these, polyethylene terephthalate films are particularly preferred in terms of heat resistance during film formation and curing of the curable resin layer 11.

[0023] The haze of the substrate 10 is preferably not more than 5. The thinner the thickness of the substrate 10, the more advantageous it is from an economical standpoint, but in consideration of the function of maintaining strength, the thickness is preferably 10 μm to 30 μm.

[0024] <Curable resin layer> The curable resin layer 11 contains a curable resin composition including (A) a binder polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a polymerization initiator.

[0025] (A) Binder polymer The binder polymer (A) preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and is further preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Furthermore, the binder polymer (A) may be thermoplastic.

[0026] The (A) binder polymer is represented by the following formula (I):

number

[0027] Tg total If Tg is low, the curable resin layer 11 formed will be loose, and edge fusing will become a problem when the laminated film 1 is stored in a roll. Also, tack will increase. total If the viscosity is high, the melt viscosity of the curable resin layer 11 increases, and the adhesive strength to the surface of the building material decreases, for example, when the laminated film 1 is thermocompressed to the surface of a building material, for example, a base material 110 made of an inorganic material. From the above viewpoint, the weight average value Tg of the glass transition temperature Tg of (A) binder polymer total The temperature is preferably 55°C or higher and 120°C or lower, and more preferably 55°C or higher and 85°C or lower.

[0028] When a mixture of multiple polymers is used as the binder polymer (A), the glass transition temperature is determined as the average value of all the polymers.

[0029] Glass transition temperature Tg i When calculating the glass transition temperature of a homopolymer consisting of comonomers that form the corresponding binder polymer, the value shown in "Polymer handbook, Third edition, John Wiley & Sons, 1989, p. 209 Chapter VI 'Glass transition temperatures of polymers'" edited by Brandrup, J. and Immergut, EH shall be used.

[0030] Tg of representative comonomers i are as follows (all literature values): Methacrylic acid: Tg=501K Benzyl methacrylate: Tg=327K Methyl methacrylate: Tg=378K Styrene: Tg=373K 2-Ethylhexyl acrylate: Tg=223K The glass transition temperature (Tg total ) is preferably a copolymer of an acid monomer and another monomer.

[0031] The weight-average molecular weight of the (A) binder polymer is preferably 5,000 to 500,000. From the viewpoint of maintaining a uniform thickness of the curable resin layer 11, the weight-average molecular weight of the (A) binder polymer is preferably 5,000 or more, and from the viewpoint of maintaining the curability of the curable resin layer 11, the weight-average molecular weight is preferably 500,000 or less. The weight-average molecular weight (Mw) of the (A) binder polymer is more preferably 10,000 to 200,000, and even more preferably 20,000 to 100,000 or 23,000 to 50,000. Furthermore, the dispersity (Mw / Mn) of the (A) binder polymer, which is the ratio of the Mw to the number-average molecular weight (Mn) of the (A) binder polymer, is preferably 1.0 to 6.0.

[0032] The (A) binder polymer is preferably obtained by polymerizing at least one kind of first monomer described below, and more preferably obtained by copolymerizing at least one kind of first monomer with at least one kind of second monomer described below.

[0033] The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, β-carboxyethyl (meth)acrylate, and maleic acid half ester. Among these, (meth)acrylic acid is particularly preferred.

[0034] Examples of the second monomer include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), (meth)acrylic acid alkyl esters, (meth)acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, crosslinkable monomers, etc. Among these, unsaturated aromatic compounds are preferred.

[0035] Examples of unsaturated aromatic compounds include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), etc. Among these, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

[0036] The (meth)acrylic acid alkyl ester is a concept that encompasses both chain alkyl esters and cyclic alkyl esters, and specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0037] Examples of (meth)acrylic acid aralkyl esters include benzyl (meth)acrylate, and examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Examples of polar monomers include hydroxy group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and penteneol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate.

[0038] Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

[0039] The binder polymer (A) can be prepared by subjecting the first monomer and / or the second monomer to a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0040] The (A) binder polymer contains a (meth)acrylic resin, and preferably contains benzyl (meth)acrylate as a monomer component. This makes it possible to suitably control the balance between adhesion to the substrate and adhesion to building materials, for example, base materials mainly composed of inorganic materials.

[0041] The content of (A) binder polymer in the curable resin composition (based on the total solid content of the curable resin composition. Unless otherwise specified, this applies to each component) is preferably in the range of 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 60% by mass. The content of (A) binder polymer is preferably 10 to 90% by mass.

[0042] (B) Compounds having an ethylenically unsaturated bond (B) The compound having an ethylenically unsaturated bond is a compound that has polymerizability due to having an ethylenically unsaturated bond, specifically an ethylenically unsaturated group, in its structure. The curable resin composition may have one or more ethylenic double bonds as component (B), and it is preferable to use a compound having two or more ethylenic double bonds.

[0043] Specific examples of the component (B) include di(meth)acrylates of polyalkylene glycols in which an average of 2 to 15 moles of alkylene oxide are added to both ends of bisphenol A, tri(meth)acrylates of polyalkylene triols in which an average of 3 to 25 moles of alkylene oxide are added to trimethylolpropane, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and polyalkylene oxide groups are added to isocyanurate rings, and ε- Examples of suitable compounds include compounds obtained by converting alcohols obtained by modifying them with caprolactone into (meth)acrylates, compounds obtained by directly reacting these with (meth)acrylic acid without modifying them with an alkylene oxide group or ε-caprolactone, tetra(meth)acrylates of polyols in which an average of 4 to 35 moles of alkylene oxide are added to pentaerythritol, and hexa(meth)acrylates of polyols in which an average of 4 to 30 moles of alkylene oxide are added to dipentaerythritol. These compounds can be used alone or in combination of two or more.

[0044] Component (B) preferably contains a difunctional monomer and a tetrafunctional monomer, which increases the surface strength of the laminated film after adhesion.

[0045] The content of the (B) compound having an ethylenically unsaturated group in the curable resin composition is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 30% by mass to 50% by mass. The content of the (B) compound having an ethylenically unsaturated group is preferably 5% by mass or more from the viewpoint of suppressing poor curing of the curable resin layer 11, and is preferably 70% by mass or less from the viewpoint of suppressing delay in peeling of the cured resin film.

[0046] (C) Polymerization initiator Examples of the polymerization initiator (C) in the present invention include a thermal polymerization initiator and a photopolymerization initiator. The thermal polymerization initiator is not particularly limited, but examples thereof include azobis compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis2,4-dimethylvaleronitrile, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(cyclohexane-1-carbonitrile), 1,1'-azobis(1-acetoxy-1-phenylethane), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); and peroxydicarbonates such as benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis-(4-t-butylcyclohexyl)peroxydicarbonate, and diisopropyl peroxydicarbonate. These can be used alone or in combination of two or more.

[0047] The photopolymerization initiator is a compound that generates radicals when exposed to actinic rays and can polymerize (B) a compound having an ethylenically unsaturated group, etc. The curable resin composition may contain a photopolymerization initiator that is generally known in the technical field.

[0048] Examples of the photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0049] Examples of the hexaarylbiimidazole compound include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenyl Biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,Examples include 2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole and 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole. Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoints of curability and adhesion.

[0050] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. N-phenylglycine is particularly preferred because of its high sensitizing effect.

[0051] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0052] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of use as a sensitizer and adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0053] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. Commercially available acylphosphine oxide compounds include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

[0054] Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0055] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

[0056] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of curability, availability, etc.

[0057] As the pyrazoline derivative, from the viewpoint of adhesion, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline are preferred.

[0058] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0059] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred.

[0060] The content of the polymerization initiator (C) in the curable resin composition is preferably 1.5 to 15 mass %, more preferably 2.0 to 10 mass %, based on the total of the components (A) to (C). By adjusting the content of the polymerization initiator (C) within the above range, sufficient curability can be obtained. When the (C) polymerization initiator is a thermal polymerization initiator, if the content of the (C) polymerization initiator is too high, when the laminated film 1 is thermocompressed onto the surface of a building material, for example, a base material 110 whose main component is an inorganic material, the laminated film 1 will begin to harden due to the heat of the heat roll, making it difficult for the laminated film 1 to adhere to the surface of the base material 110.

[0061] The curable resin composition preferably uses a hexaarylbisimidazole compound, which is a photopolymerization initiator, as the polymerization initiator (C). In this case, the content of the hexaarylbisimidazole compound in the curable resin composition is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.

[0062] As the (C) polymerization initiator, it is preferable to use an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone in combination with a hexaarylbisimidazole compound. In this case, the content of the aromatic ketone compound in the curable resin composition is preferably 0.5 mass% or less, more preferably 0.01 mass% to 0.4 mass%, and the content of the hexaarylbisimidazole compound in the curable resin composition is preferably 0.1 mass% to 10 mass%, more preferably 0.5 mass% to 5 mass%.

[0063] The curable resin composition preferably contains 0 to less than 10 parts by mass of the reactive oligomer having one or more unsaturated groups per 100 parts by mass of component (A), and the amount of the reactive oligomer having one or more unsaturated groups is preferably below the detection limit. That is, the curable resin composition preferably does not substantially contain the reactive oligomer having one or more unsaturated groups. Examples of reactive oligomers having one or more unsaturated groups include urethane (meth)acrylate compounds, epoxy (meth)acrylate compounds, and polyester (meth)acrylate compounds, and the above content is the total content of these compounds.

[0064] Furthermore, a filler may be blended into the curable resin composition for the purposes of improving filling properties, suppressing shrinkage during curing, improving smoothness, and the like. Such fillers can have an average particle size of 0.01 μm or more and 100 μm or less, and examples thereof include powders of silicon oxide, magnesium oxide, calcium oxide, sodium carbonate, calcium carbonate, sodium bicarbonate, etc. Among these, calcium carbonate powder is preferred in terms of its affinity with lightweight aerated concrete (ALC), and its average particle size is preferably 0.1 to 20 μm, and particularly preferably 0.1 to 10 μm. The average particle size of the filler is measured by laser diffraction.

[0065] The content of the filler in the curable resin composition is preferably 10 to 1000 parts by weight, particularly preferably 30 to 500 parts by weight, and even more preferably 50 to 200 parts by weight, when the total of components (A) to (C) is 100 parts by weight. If the filler content is too low, the resin shrinkage and fluidity will be too great, making it difficult to achieve the desired smoothness. If the filler content is too high, the uncured film will become brittle, reducing adhesion, and the cured film will become brittle, tending to cause the resin and filler to fall off from the surface.

[0066] <Other ingredients> The resin composition preferably contains additives such as a pigment, an antioxidant, and a stabilizer, if desired.

[0067] Examples of dyes include tris(4-dimethylaminophenyl)methane (leuco crystal violet), bis(4-dimethylaminophenyl)phenylmethane (leucomalachite green), fuchsin, phthalocyanine green, auramine base, paramagienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Eizen® MALACHITE GREEN, manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20, and diamond green (Eizen® DIAMOND GREEN GH, manufactured by Hodogaya Chemical Co., Ltd.). Among these, diamond green and leuco crystal violet are preferred from the viewpoint of improving coloring properties, hue stability, and color development after exposure. These may be used alone or in combination of two or more.

[0068] The content of the dye in the resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and even more preferably in the range of 0.04% by mass to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and on the other hand, is preferably 3% by mass or less from the viewpoint of maintaining the curability of the curable resin layer 11.

[0069] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K). These may be used alone or in combination of two or more.

[0070] The content of the antioxidant in the resin composition is preferably in the range of 0.01% by mass to 3.0% by mass, more preferably in the range of 0.05% by mass to 2.0% by mass. The content of the antioxidant is preferably 0.05% by mass or more from the viewpoint of improving the curability and durability of the curable resin layer 11, and is preferably 2.0% by mass or less from the viewpoint of improving adhesion.

[0071] The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These may be used alone or in combination of two or more.

[0072] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (e.g., aluminum salt with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamine. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. These can be used alone or in combination of two or more.

[0073] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.

[0074] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass. This total content is preferably 0.001% by mass or more in order to impart good storage stability to the resin composition, and is preferably 3% by mass or less in order to maintain the curability of the curable resin layer 11.

[0075] The curable resin layer 11 may comprise or consist of a curable resin composition. The thickness of the curable resin layer 11 in the laminated film 1 of this embodiment is 20 μm or more, preferably 50 μm or more, and more preferably 80 μm to 500 μm. If the thickness is too thin, the curable resin composition component in the laminated film will not flow into the irregularities of the inorganic substrate in sufficient amount, failing to sufficiently cover the inorganic substrate surface, or the number of layers required to obtain a thickness appropriate for mechanically protecting the substrate surface, for example, the surface of an ALC panel, will be too large, making the lamination process complicated and the cost too high, or an appropriate thickness for protection will not be obtained, making it difficult to prevent damage to the substrate surface.Furthermore, if the thickness is too thick, edge fuse will be more likely to occur during roll film production, the coating film will break, or it will be more likely to peel off from the substrate surface, resulting in excessively high costs.

[0076] The laminated film 1 of this embodiment preferably has an adhesion of 3 gf or more and less than 30 gf in a tackiness test when polyethylene terephthalate is used as the substrate 10. This provides the laminated film 1 with better tack to the substrate 10. The tackiness test values ​​are measured by the method described in the examples below.

[0077] In the laminated film 1 of this embodiment, in a cross-cut test in accordance with JIS K 5400, the ratio of the peeled area of ​​the curable resin layer 11 to the base material is preferably less than 20%. This provides the laminated film 1 with better adhesion to the substrate 10. The cross-cut test values ​​are measured by the method described in the examples below.

[0078] The laminated film 1 of this embodiment preferably has a press flow value of 500 μm to 2000 μm relative to the base material in a press flow test. If this value is large, the adhesive strength with the substrate 10 will be strong, making it easier for part of the cured resin film 11' to be removed when the substrate 10 is peeled off, and edge fusing will be more likely to occur when producing a roll film, making long-term storage difficult. Also, if this value is small, the amount of resin flowing onto the base material surface will decrease, resulting in reduced adhesion to the base material. The values ​​obtained in the press flow test are measured by the method described in the examples below.

[0079] <Cover film> As shown in FIG. 1, the laminated film 1 may include a cover film 12 disposed on the side of the curable resin layer 11 opposite to the side on which the substrate 10 is disposed. The cover film 12 serves as a protective film to prevent the laminated film 1 from being scratched, stained, or chipped during storage and transportation.

[0080] An important characteristic of the cover film 12 used in the laminate film 1 is that it has an appropriate adhesive strength. That is, it is preferable that the adhesive strength of the cover film 12 to the curable resin layer 11 is sufficiently smaller than the adhesive strength of the substrate 10 to the curable resin layer 11, so that the cover film 12 can be easily peeled off from the laminate film 1.

[0081] As such a cover film 12, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, or the like can be used. The thickness of the cover film 12 is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0082] A release layer suitable for peeling the cover film 12 from the curable resin layer 11 may be provided on one side of the cover film 12. Release layers are generally classified into silicone compounds and non-silicone compounds. Examples of silicone compounds include condensation reaction-type silicone resins obtained by reacting a polydimethylsiloxane having silanol groups at both ends with a polymethylhydrogensiloxane or a polymethylmethoxysiloxane, addition reaction-type silicone resins obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with a polymethylhydrogensiloxane, ultraviolet-curable or electron-beam-curable silicone resins obtained by curing an acrylic silicone or an epoxy group-containing silicone with ultraviolet light or an electron beam, and modified silicone resins such as epoxy-modified silicone resins (silicone epoxy), polyester-modified silicone resins (silicone polyester), acrylic-modified silicone resins (silicone acrylic), phenol-modified silicone resins (silicone phenol), alkyd-modified silicone resins (silicone alkyd), and melamine-modified silicone resins (silicone melamine). Examples of non-silicone compounds include alkyd resins, long-chain alkyl resins, acrylic resins, and polyolefin resins.

[0083] The thickness of the release layer is preferably in the range of 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. If the thickness exceeds 2 μm, the appearance of the coating may deteriorate and the coating may not be sufficiently cured, and if the thickness is less than 0.001 μm, sufficient releasability may not be obtained.

[0084] [Laminated film manufacturing method] The laminated film 1 of the present embodiment as described above can be produced by the following steps: adding a solvent to the curable resin composition to prepare a curable resin composition solution; A step of applying a curable resin composition solution onto a substrate 10; and The curable resin layer 11 can be produced by a production method including a step of drying a curable resin composition solution to form the curable resin layer 11 on the substrate 10. As the method, a known method can be adopted.

[0085] First, the curable resin composition used for the curable resin layer 11 is mixed with a solvent that dissolves it to form a uniform resin composition solution (coating liquid). Suitable solvents include organic solvents such as ketones typified by acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. The solvent is preferably added to the curable resin composition so that the viscosity of the resin composition solution is 500 mPa·sec to 4000 mPa·sec at 25°C.

[0086] Next, the coating liquid is applied onto the substrate 10 using a bar coater or a roll coater. Next, the resin composition solution applied onto the substrate 10 is dried to remove the solvent (organic solvent), thereby forming a curable resin layer 11 on the substrate 10.

[0087] The amount of organic solvent remaining in the curable resin layer 11 is preferably 0.5 parts by mass to 5 parts by mass based on 100 parts by mass of the curable resin layer 11. This can improve the applicability of the laminate film 1 to a base material, such as an ALC panel.

[0088] If necessary, a cover film 12 (protective film) may be laminated on the surface of the curable resin layer 11.

[0089] The laminated film 1 can be suitably used as a construction material, for example, as a base material 110 mainly composed of an inorganic material, for surface coating of concrete, particularly for surface coating of lightweight aerated concrete (ALC) panels.

[0090] [Structure] FIG. 2 is a cross-sectional view showing an example of the structure of the present invention. The structure 100 is formed by laminating the laminated film on a building material. The structure 100 shown in FIG. 2 includes a base material 110 containing an inorganic material as a main component, and a curable resin layer 11 formed on the base material 110 as a building material. The base material 110, which is mainly composed of an inorganic material, is, for example, a panel made of concrete or lightweight foam concrete (ALC).

[0091] In the structure 100, the base material 110 preferably has a sealant layer 111 containing a sealer (primer) on the surface on the curable resin layer 11 side. This reduces powdering on the surface of the ALC panel, improves adhesion to the curable resin layer 11 of the laminate film 1, and increases the adhesion area between the ALC panel and the curable resin layer 11 of the laminate film 1. This allows the laminate film 1 to be more firmly attached to the surface of the ALC panel.

[0092] Sealers include synthetic rubber-based sealers, acrylic-based sealers, urethane-based sealers, epoxy-based sealers, silicone resin-based sealers, silane-based sealers, etc., and are not particularly limited. However, acrylic resin emulsion sealers (EM sealers) are preferred because they are inexpensive and provide good adhesion.

[0093] [Structure fabrication method] 3(a) to 3(c) are cross-sectional views illustrating how the laminated film is attached to the surface of a concrete panel. The structure 100 is fabricated by the following steps: A step of laminating the curable resin layer 11 of the laminated film 1 on the base material 110; and a step of exposing the curable resin layer 11 to light or heating the curable resin layer 11 to cure the curable resin layer 11 to form a cured resin film 11'; It can be produced by a production method including the steps of:

[0094] The following describes a method for covering the surface of an ALC panel as a base material 110 made of an inorganic material using the laminated film 1.

[0095] The surface properties of ALC panels vary depending on the manufacturer or lot, but they can be coated directly on their surface, or they can be polished with sandpaper or the like to expose the internal foamed portion before coating.

[0096] First, as shown in Fig. 3(a), the laminate film 1 is laminated and attached onto the ALC panel with the curable resin layer 11 facing the ALC panel. The laminate film 1 may be attached directly to the surface of the ALC panel, or the ALC panel may be preheated or dried before the laminate film 1 is attached.

[0097] When the laminated film 1 has a cover film 12, the curable resin layer 11 is laminated and attached to the ALC panel while or after peeling off the cover film 12.

[0098] When attaching, the laminated film 1 can be attached onto the ALC panel while pressing it with a roll having a surface temperature of 70° C. or higher (hereinafter also referred to as a hot roll).

[0099] The surface temperature of the heated roll in this case is preferably 80°C or higher, particularly preferably 100°C to 200°C, and even more preferably 130°C to 190°C. If the surface temperature of the heated roll is too low, the curable resin layer 11 of the laminated film 1 does not soften or melt sufficiently, making it difficult for the curable resin layer 11 to fully penetrate the surface of the ALC panel, which tends to cause the curable resin layer 11 to peel off after curing. If the surface temperature of the heated roll is too high, the components in the curable resin layer react and do not fully melt, resulting in insufficient penetration into the surface of the ALC panel and a decrease in adhesive strength, or the curable resin layer 11 melts too much, reducing its viscosity and resulting in complete penetration into the ALC panel, leaving no resin component to coat the surface.

[0100] The linear pressure of the heated roll when pressing the laminated film 1 is preferably 0.1 to 100 kg / cm, particularly preferably 0.3 to 50 kg / cm, and even more preferably 0.5 to 25 kg / cm. The moving speed of the heated roll relative to the laminated film 1 is preferably 0.01 to 20 m / min, particularly preferably 0.1 to 15 m / min, and even more preferably 0.2 to 10 m / min.

[0101] If the linear pressure applied by the heated roll is too small or the moving speed of the heated roll is too high, the curable resin layer 11 of the laminated film 1 will not penetrate sufficiently into the surface of the ALC panel, which will tend to cause peeling of the cured curable resin layer 11. Also, if the linear pressure applied by the heated roll is too large or the moving speed of the heated roll is too slow, the curable resin layer 11 will tend to penetrate completely into the ALC panel, leaving no resin to coat the surface.

[0102] When attaching the laminated film 1 to the ALC panel, a hand heater, an iron, etc. can be used in addition to the above-mentioned heated roll.

[0103] Prior to the step of attaching the laminated film 1 to the ALC panel, a step of applying a sealant (primer) or the like to the surface of the ALC panel to form a sealant layer may be included.

[0104] Next, as shown in Figure 3(b), when the curable resin composition contains a photopolymerization initiator as a polymerization initiator (C), the laminated film 1 is laminated on the surface of the ALC panel and exposed to light, for example, sunlight, for a predetermined period of time, thereby curing the curable resin composition and forming a resin cured film 11' on the surface of the ALC panel.

[0105] In this case, since the thickness of the cured resin film 11' is 50 μm or more, the surface of the ALC panel can be sufficiently protected, and the cured resin film 11' is also suitably prevented from breaking or peeling off from the surface of the ALC panel.

[0106] 3(c), the substrate 10 of the laminate film 1 is peeled off from the surface of the cured resin film 11'. At this time, in the laminate film 1 of the present embodiment, the adhesion between the substrate 10 and the curable resin layer 11 is appropriately controlled, so that the cured resin film 11' is prevented from being carried away by the substrate 10 and peeled off, and deterioration of the appearance is suppressed.

[0107] Furthermore, in the laminated film 1 of this embodiment, the adhesion to the curable resin layer 11 of the base material 110 (ALC panel) is appropriately controlled, so that while it has sufficient adhesion to the ALC panel surface, it does not follow the unevenness present on the panel surface, and the unevenness does not stand out on the surface of the resin cured film 11', thereby suppressing deterioration in appearance.

[0108] That is, the laminated film 1 of the present invention achieves excellent adhesion to inorganic materials while controlling adhesion to the substrate 10.

[0109] The substrate 10 of the laminated film 1 may remain laminated on the surface of the curable resin layer 11 without being peeled off from the surface of the cured resin film 11'.

[0110] Unless otherwise specified, the evaluation values ​​of the various parameters described above are measured values ​​in accordance with the measurement methods in the examples described below.

[0111] Although the embodiment of the present invention has been described above, the present invention is not limited to this and can be modified as appropriate within the scope of the invention.

[0112] For example, a design feature may be imparted to the cured resin layer that covers the surface of the base material. Specifically, for example, a pattern for design purposes may be provided on the surface of the substrate, and this pattern may be transferred to a resin layer that covers the surface of the base material after curing. This allows the surface of the base material to be given a design feature and improves its aesthetic appearance.

[0113] Furthermore, if the base material has joints (such as the joints in concrete structures, panel joints in ALC panels or siding materials, or joints that occur where other materials such as concrete and ALC panels meet, or unnecessary design grooves), the gaps and unevenness that occur in the joints, as well as thinning (dents) in the sealant filled in the joints, can create unevenness on the surface of the base material, significantly reducing its aesthetic appeal. However, by covering these joints with a resin layer, the resin layer, which has an adjusted binder polymer composition and glass transition temperature, adheres to the surface of the base material without completely conforming to the gaps, unevenness, or thinning of the sealant that occur in the joints, and can absorb the unevenness on the surface of the base material and make it closer to flat, thereby improving the aesthetic appeal of the structure, including the joints. [Example]

[0114] Next, the present embodiment will be described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples as long as it does not deviate from the gist of the present embodiment. Physical properties in the examples were measured by the following methods.

[0115] <1. Preparation of Resin Composition> Photosensitive resin compositions were prepared by mixing the compounds shown in Tables 1 and 2. The values ​​in Tables 1 and 2 are solid content amounts.

[0116] <2. Preparation of laminated film> Acetone solvent was added to the curable resin composition until the solid content reached 58% by mass, and the mixture was thoroughly stirred and mixed. The solution of the curable resin composition was uniformly applied to a 25 μm thick polyethylene terephthalate film (Toray FB-40; 16 μm polyethylene terephthalate (LDPE) film) as a substrate using a bar coater, and dried for a predetermined time in a dryer at 95 ° C. to form a curable resin layer (dry film) with a thickness of 30 μm to 240 μm. Next, a 33 μm thick polyethylene film (Tama Poly GF-858) was laminated on the surface of the curable resin layer as a cover film to obtain a laminated film.

[0117] <3. Evaluation Method> (1) Appearance evaluation In a dark place, the cover film of the laminate film was peeled off, and the laminate film was attached to the surface of an ALC panel (Asahi Kasei Construction Materials Corporation's "Hebel Powerboard Flat Panel" (thickness 37 mm)) by pressing it with a rubber roll heated to 180°C at a linear pressure of 2 kg / cm. After attachment, the panel laminate was left in sunlight for 1 hour to cure the curable resin composition. The polyester film was then peeled off from the laminate film. The appearance of the cured resin film after peeling was observed and ranked as follows: The evaluation criteria are as follows: ◎: The cured resin film is not absorbed by the substrate at all, and the surface is smooth. ◯: The cured resin film is not carried to the substrate, but the surface is slightly uneven. △: The cured resin film is slightly taken over by the substrate, and the surface is slightly uneven. ×: The cured resin film is completely removed to the substrate, and the substrate surface is exposed

[0118] (2) Tackiness In a dark place, while peeling off the cover film from the laminate film, the laminate film was laminated onto the substrate using a hot roll laminator (AL-700, manufactured by Asahi Kasei Engineering Co., Ltd.) at a roll temperature of 105°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min. After leaving the laminate film at 23°C and 50% relative humidity for 24 hours, the 1-inch-wide support layer (in this example, a PET film) was peeled off at a 180° angle, and its strength was measured using a Tensilon RTM-500 (manufactured by Toyo Seiki Seisakusho) and ranked as follows: ○: PET adhesion is 3gf or more and less than 30gf △: PET adhesion is 30gf or more and less than 50gf ×: PET adhesion is 50 or more

[0119] (3) Cross-cut test Powder on the surface of an ALC panel ("Hebel Power Board Flat Panel" manufactured by Asahi Kasei Construction Materials Co., Ltd., thickness 37 mm) was removed using a blower. In a dark place, the cover film of the laminate film was peeled off, and the laminate film was attached to the surface of a concrete panel while tracing the surface with a linear pressure of 2 kg / cm using a hand heater heated to 180°C. Heating was completed after two round trips (1 minute). After attachment, the panel laminate was allowed to cool for 30 minutes to 1 hour. The panel laminate was left under sunlight for 1 hour to cure the curable resin composition. The substrate film was then peeled off from the laminate film to obtain a panel laminate for evaluation. Two linear cuts were made in the shape of a cross on the surface of the resin cured film (coating layer) of the panel laminate obtained above using a cutter knife, and commercially available gummed tape was attached so as to cover the center of the intersection of the cuts. A 5 kg roll was then moved back and forth 10 times to completely attach the tape. The gummed tape was peeled off from the edge at a constant speed of 10 m / min. The adhesions on the peeled gummed tape were observed and ranked as follows: ○: No peeling was observed in the cut area △: Slight peeling was observed at the cut area ×: The cut part was completely peeled off

[0120] (4) Press flow The prepared laminated film was cut into a 2.5 cm square, the cover film was peeled off, and then the film was sandwiched between the center of a 10 cm square polyethylene terephthalate film, and a force of 100 kg was applied for 5 minutes using a hydraulic press heated to 40°C. The protrusion width of the curable resin layer was then measured in four directions (a total of eight points), and the average value was calculated. This test was carried out with n = 2, and the average value of n = 2 was calculated and used as the value of the press flow test. The press flow value was ranked as follows: ○: 500~2000um ×: Less than 500um or 2000um or more

[0121] For each example and comparative example, the composition of the photosensitive resin composition and the evaluation results of the laminate are shown in Tables 1 and 2. In addition, the names of the components represented by abbreviations in Tables 1 and 2, the solvents used, etc. are shown in Table 3.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] As shown in Tables 1 and 2, the binder polymers contained components (A) to (C), and the weight average glass transition temperatures (Tg) of the binder polymers were total The laminated films of the examples, in which the curing temperature was 55 to 120°C and the thickness of the curable resin layer was 20 μm or more, showed good results in the press flow test, tack test, and cross-cut test. In addition, there was no peeling of the cured resin film, and no deterioration in appearance due to peeling was observed.

[0126] In contrast, in Comparative Example 1, which did not contain a polymerization initiator, the curable resin layer did not cure sufficiently, and sufficient adhesion and bonding to the ALC panel (base material) was not obtained. In Comparative Example 2, in which the curable resin layer was thin, the cured film broke, and sufficient adhesion to the ALC panel was not obtained. In Comparative Example 3, which contained a large amount of thermal polymerization curing agent, the curable resin layer began to cure during thermocompression bonding to the ALC panel, and it was difficult for the resin to adhere to the ALC panel. Tg total In Comparative Example 4, where Tg was low, press flow was large, raising concerns about edge fuse. Because of the high tackiness with PET, when the substrate was peeled off, the cured resin film was taken to the substrate (peeled off), resulting in a deterioration in appearance. total In Comparative Example 5, in which the temperature was high, the curable resin layer did not easily flow into the ALC panel during thermocompression bonding, and sufficient adhesion to the ALC panel was not obtained.

[0127] Although the embodiment of the present invention has been described above, the present invention is not limited to this and can be modified as appropriate within the scope of the invention. [Industrial Applicability]

[0128] By using the laminated film according to the present invention, it is possible to control adhesion to the substrate while realizing excellent adhesion to inorganic materials, and the laminated film can be widely used as a laminated film that covers and protects the surface of a base material whose main component is an inorganic material. [Explanation of symbols]

[0129] 1: Laminated film 10: Base material 11: Curable resin layer 11': Resin cured film 12: Cover film 100: Structure 110: Base material 111: Sealant layer

Claims

1. A substrate and a curable resin layer laminated on the substrate, The curable resin layer comprises the following components (A) to (C): (A) a binder polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a polymerization initiator, Including, The polymerization initiator (C) contains a curable resin composition containing an imidazole compound as a photopolymerization initiator, The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) ｔｏｔａｌ is 55°C or higher and 120°C or lower, the curable resin composition has a total content of a urethane (meth)acrylate compound and a polyester (meth)acrylate compound of 0 parts by mass or more and less than 10 parts by mass, based on 100 parts by mass of the component (A); A laminated film, characterized in that the thickness of the curable resin layer is 20 μm or more.

2. A substrate and a curable resin layer laminated on the substrate, The curable resin layer comprises the following components (A) to (C): (A) a binder polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a polymerization initiator, Including, The component (A) contains a curable resin composition that includes a (meth)acrylic resin and benzyl (meth)acrylate as a monomer component, and the laminated film for coating a surface of a building material contains the curable resin composition, The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) ｔｏｔａｌ is 55°C or higher and 120°C or lower, the curable resin composition has a total content of a urethane (meth)acrylate compound and a polyester (meth)acrylate compound of 0 parts by mass or more and less than 10 parts by mass, based on 100 parts by mass of the component (A); A laminated film, characterized in that the thickness of the curable resin layer is 20 μm or more.

3. The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) ｔｏｔａｌ The laminated film according to claim 1 or 2, wherein the temperature is 55°C or higher and 100°C or lower.

4. The weight average value Tg of the glass transition temperature Tg of the binder polymer (A) ｔｏｔａｌ The laminated film according to claim 1 or 2, wherein the temperature is 55°C or higher and 85°C or lower.

5. The curable resin composition has a total content of a urethane (meth)acrylate compound and a polyester (meth)acrylate compound that is less than a detection limit based on 100 parts by mass of the component (A). The laminate film according to any one of claims 1 to 4.

6. The laminated film according to any one of claims 1 to 5, wherein the thickness of the curable resin layer is 50 µm or more.

7. 7. The laminated film according to claim 1, wherein the adhesion to a substrate made of polyethylene terephthalate is 3 gf or more and less than 30 gf in a tackiness test.

8. The laminated film according to any one of claims 1 to 6, wherein the building material is a base material containing an inorganic material as a main component.

9. The laminate film according to claim 8, wherein in a cross-cut test, the ratio of the peeled area of ​​the curable resin layer to the base material containing the inorganic material as a main component is less than 20%.

10. 9. The laminated film according to claim 8, wherein the press flow value for the base material containing the inorganic material as a main component is 500 to 2000 μm in a press flow test.

11. In the curable resin layer, The content of the component (A) is 20% by mass to 80% by mass, The content of the component (B) is 20% by mass to 60% by mass, The content of the component (C) is 3.0% by mass to 10% by mass. The laminated film according to any one of claims 1 to 10.

12. The laminate film according to any one of claims 1 to 11, wherein the thickness of the curable resin layer is 80 to 500 µm.

13. The laminate film according to any one of claims 1 and 3 to 12, wherein the component (A) contains a (meth)acrylic resin and contains benzyl (meth)acrylate as a monomer component.

14. The laminate film according to any one of claims 1 to 13, wherein the component (B) contains a difunctional monomer and a tetrafunctional monomer.

15. The laminate film according to any one of claims 1 to 14, further comprising a cover film disposed on the side of the curable resin layer opposite to the side on which the substrate is disposed.

16. The laminate film according to any one of claims 1 to 15, wherein the curable resin composition further contains a dye.

17. the curable resin composition contains an organic solvent, The laminate film according to any one of claims 1 to 16, wherein the amount of the organic solvent remaining in the curable resin layer is 0.5 parts by mass to 5 parts by mass based on 100 parts by mass of the curable resin layer.

18. The laminate film according to any one of claims 1 to 17, wherein the polymerization initiator (C) is 2.5 parts by mass to 15 parts by mass relative to the total of the components (A) to (C).

19. The laminate film according to any one of claims 2 to 18, comprising a photopolymerization initiator as the (C) polymerization initiator.

20. The laminate film according to claim 19, comprising an imidazole compound as the photopolymerization initiator.

21. A structure comprising the building material and the laminate film according to any one of claims 1 to 20 laminated on the building material.

22. The structure according to claim 21 , wherein the building material includes a sealant layer (resin layer) on the surface on the laminated film side.

23. 23. The structure according to claim 21 or 22, wherein the building material is a matrix mainly composed of an inorganic material.

24. A step of laminating the curable resin layer side of the laminate film according to any one of claims 1 to 20 onto the building material; and curing the curable resin layer with light or heat to form a cured resin film.

25. 25. The method for producing a structure according to claim 24, wherein the building material is a base material whose main component is an inorganic material.

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