Method for manufacturing a laminate and laminate

Abstract

The object of this invention is to provide a method for easily attaching a functional film having an adhesive layer to the surface of an inorganic substrate such as concrete. [Solution] The present invention relates to a laminate comprising: step A, forming a layer 1 containing cement and a cationic resin on an inorganic substrate; step B, forming a layer b on layer a containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin; and step C, attaching a film or sheet having an adhesive layer or a tack layer to layer b via the adhesive layer or tack layer.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing a laminate by attaching a functional film or sheet to an inorganic substrate, and to a laminate itself. [Background technology]

[0002] There are known spalling prevention sheets that adhere to and cover the surface of structures having a water-absorbing inorganic material surface, such as reinforced concrete structures, to prevent concrete fragments and other materials from peeling off and falling from these structures. As a method for installing such a peeling prevention sheet, it is known that the following steps are taken: using a disc sander (rotating cutting wheel) or the like to grind off any protrusions from the surface of the reinforced concrete structure and make it smooth; if there are any cross-sectional defects on the surface of the reinforced concrete structure, they are filled and repaired with mortar or putty, and if necessary, surface treatment steps such as waterproofing treatment for leaks are performed; then a primer application step is performed to apply a primer to the surface of the reinforced concrete structure that has been smoothed in the surface treatment step to improve adhesion; then an adhesive application step is performed to apply the adhesive for bonding the peeling prevention sheet to the surface of the reinforced concrete structure to which the primer was applied in the previous step; and finally, a sheet application step is performed to attach the peeling prevention sheet (Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6203441 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the conventional construction methods described above, there is a risk of asbestos dispersion during the process of removing protrusions from the surface of reinforced concrete structures to create a smooth surface. Furthermore, this process requires special handling by workers with asbestos handling qualifications. Therefore, it is desirable to minimize or eliminate the need for processing these protrusions as much as possible. However, while the process of removing protrusions to create a smooth surface is complicated, there is no known simple method, such as attaching a functional film with an adhesive layer to the surface of an inorganic substrate like concrete, nor is there any known method to make it difficult to peel off. The present invention aims to provide a method for easily and securely attaching a functional sheet or film having an adhesive layer to the surface of an inorganic substrate such as concrete, while minimizing the need for surface smoothing treatment. [Means for solving the problem]

[0005] As a result of diligent research to solve the aforementioned problems, the inventors have found that the problems can be solved by forming a layer containing cement and cationic resin on an inorganic substrate, and have completed the present invention.

[0006] In other words, the method for manufacturing a laminate of the present invention comprises: step A, forming a layer a containing cement and a cationic resin on an inorganic substrate; step B, forming a layer b on layer a containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin; and step C, attaching a layer s comprising an adhesive layer or tack layer and a film or sheet onto layer b via the adhesive layer or tack layer.

[0007] Furthermore, the present invention provides a method for manufacturing a laminate, comprising: step X, applying an aqueous sealer or styrene-acrylic copolymer emulsion to an inorganic substrate to form a layer x; step A, forming a layer a containing cement and a cationic resin; step B, forming a layer b on layer a containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin; and step C, attaching a layer s comprising an adhesive layer or tack layer and a film or sheet to layer b via the adhesive layer or tack layer.

[0008] The present invention preferably includes one or more steps Y between steps B and C to further form the layer b containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin.

[0009] The cationic resin used in the method for producing the laminate of the present invention is preferably a cationic acrylic copolymer or a cationic styrene-butadiene rubber.

[0010] The inorganic substrate used in the method for manufacturing the laminate of the present invention is preferably a substrate containing at least one of cement, mortar, or slate.

[0011] The laminate used in the method for manufacturing the laminate of the present invention is preferably a functional laminate.

[0012] Preferably, the function of the functional laminate used in the method for manufacturing the laminate of the present invention is a radiative cooling function and / or a heat shielding function.

[0013] The laminate of the present invention comprises an inorganic substrate, a layer a containing cement and a cationic resin, a layer b containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin, and a layer s comprising an adhesive layer or tack layer and a functional layer, all laminated in this order.

[0014] Alternatively, the laminate of the present invention is laminated in this order from an inorganic base material, a layer x obtained by applying and drying an aqueous sealer or an aqueous styrene-acrylic copolymer emulsion, a layer a containing cement and a cationic resin, a layer b containing at least one resin selected from the group consisting of moisture-curable urethane resins, aqueous acrylic resins and aqueous epoxy resins, and a layer s provided with an adhesive layer or a pressure-sensitive adhesive layer and a functional layer.

[0015] The inorganic base material in the laminate of the present invention is preferably a base material containing at least any one of cement, mortar or slate.

[0016] The cationic resin in the laminate of the present invention is preferably a cationic acrylic copolymer or a cationic styrene-butadiene rubber.

[0017] The functional layer in the laminate of the present invention is preferably a functional layer having a radiative cooling function and / or a heat shielding function. Effects of the Invention

[0018] By using the method for producing the laminate of the present invention, a commercially available film or sheet having an adhesive layer or a pressure-sensitive adhesive layer can be easily and strongly attached to an inorganic base material such as concrete while minimizing surface smoothing treatment. Furthermore, when the commercially available film or sheet having an adhesive layer or a pressure-sensitive adhesive layer is a functional film, the impartation of functionality to a structure such as concrete, which is time-consuming in conventional construction methods, can be easily and strongly performed while minimizing surface smoothing treatment. Brief Description of the Drawings

[0019] [Figure 1] It is a schematic diagram showing the laminated structure of the laminate according to one embodiment of the present invention. Mode for Carrying Out the Invention

[0020] Hereinafter, the laminate of the present invention and the method for producing the same will be described with reference to FIG. 1. A method for manufacturing a laminate according to one embodiment of the present invention comprises: step X forming a layer x obtained by applying and drying an aqueous sealer or aqueous styrene-acrylic copolymer emulsion onto an inorganic substrate; step A forming a layer a containing cement and a cationic resin; step B forming a layer b on layer a containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin; and step C attaching a layer s comprising an adhesive layer or tack layer and a film or sheet onto layer b via the adhesive layer or tack layer.

[0021] Furthermore, as shown in Figure 1, a laminate according to one embodiment of the present invention is constructed by laminating, in this order, an inorganic substrate, a layer x obtained by applying and drying an aqueous sealer or aqueous styrene-acrylic copolymer emulsion and formed on the inorganic substrate, a layer a formed on layer x containing cement and a cationic resin, a layer b provided on layer a containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin, and a layer s formed on layer b comprising an adhesive layer or tack layer and a functional layer.

[0022] Examples of inorganic substrates used in the manufacturing method of the present invention include calcium silicate boards, natural slate boards, asbestos slate boards, artificial slate boards such as glass fiber slate boards, volcanic glassy multilayer boards, magnesium oxide boards, fiber-reinforced calcium silicate molded bodies, fiber-reinforced cement molded bodies, fiber-reinforced ceramic molded bodies, concrete boards such as autoclaved lightweight concrete (ALC), mortar boards, and asphalt. Among these, substrates containing at least one of concrete, mortar, and slate are preferred. A specific example of a commercially available product is Colorbest®.

[0023] In this embodiment, layer x is a layer obtained by applying and drying an aqueous sealer or an aqueous styrene-acrylic copolymer emulsion. The aqueous sealer that can be applied to the layer x is a composition containing an aqueous resin, and the aqueous resin may be a water-soluble resin or a water-dispersible resin. The water-soluble resin is a resin that dissolves in water, and the aqueous solution of the resin is visible to the naked eye. The water-dispersible resin is a resin that exists dispersed in water, and the aqueous resin dispersion is visible to the naked eye.

[0024] Specific examples of the aqueous resin used in the aqueous sealer that can be applied to layer x include acrylic resin, vinyl resin, polyolefin resin, silicone resin, polyurethane resin, epoxy resin, phenolic resin, polyester resin, alkyd resin, polycarbonate resin, polyisocyanate compound, polyamine compound, and combinations thereof. Furthermore, two or more of these resins may be modified or graft polymerized. In addition, if the resin is in the form of dispersed particles, it may be in a single layer or a multilayer structure such as a core-shell type. The aqueous resin is preferably an aqueous epoxy resin or an aqueous acrylic resin.

[0025] The aqueous epoxy resin of the aqueous sealer that can be applied to layer x is preferably an epoxy resin having epoxy groups that is emulsified and dispersed in an aqueous medium. Specifically, examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, cresol type epoxy resin, dimer acid modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and the like.

[0026] The epoxy equivalent of the aqueous epoxy resin in the aqueous sealer that can be applied to layer x is preferably 100 g / eq or more. The epoxy equivalent of the aqueous epoxy resin is preferably 1000 g / eq or less, and more preferably 800 g / eq or less. The aforementioned epoxy equivalent refers to the number of grams (g / eq) of resin containing 1 gram equivalent of epoxy groups, and means the epoxy equivalent measured according to the manufacturer's published value or JIS K 7236 (2009).

[0027] Examples of aqueous epoxy resins for aqueous sealers that can be applied to layer x include resins obtained by emulsifying and dispersing the epoxy resin in the presence of an emulsifying component derived from polyoxyalkylene. Specifically, examples of the emulsifying component derived from polyoxyalkylene include polyoxyalkylene alkyl ether compounds such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, and polyoxyethylene oleyl ether; polyoxyalkylene alkylphenyl ether compounds such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyalkylene polycyclic phenyl ether compounds such as polyoxyethylene polycyclic phenyl ether; polyoxyalkylene alkyl ester compounds such as polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate; sorbitan compounds such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monooleate; nonionic polyoxyalkylene compounds such as polyethylene glycol and polypropylene glycol; epoxy modified products of polyoxyalkylene compounds obtained by modifying the polyoxyalkylene compound with the epoxy resin; and combinations thereof.

[0028] Examples of epoxy-modified polyoxyalkylene compounds include reaction products of polyoxyethylene glycol, an epoxy resin having hydroxyl groups and epoxy groups, a monohydric alcohol, and a compound having at least two isocyanate groups in one molecule.

[0029] Examples of epoxy resins having hydroxyl groups and epoxy groups include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, with bisphenol A type epoxy resin being particularly preferred.

[0030] The monohydric alcohol is used to block the isocyanate groups in the modified epoxy resin, and examples include ethanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

[0031] As the compound having at least two isocyanate groups in one molecule, known aliphatic, alicyclic, or aromatic polyisocyanate compounds can be used, specifically including hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and biuretized or isocyanurated compounds of these polyisocyanate compounds; and combinations thereof.

[0032] Specifically, the epoxy-modified polyoxyalkylene compound can be produced by mixing the aforementioned components and reacting them until substantially no unreacted isocyanate groups remain.

[0033] When the aqueous sealer that can be applied to layer x contains the aqueous epoxy resin, it is preferable that it also contains an aqueous polyamine compound. Specifically, examples of the aqueous polyamine compound include compounds obtained by dispersing or solubilizing a polyamine compound or a modified version thereof in water. Specifically, examples of the polyamine compound include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, triaminopropane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, and 1,3-bisaminomethylcyclohexane; aromatic polyamines such as phenylenediamine, metaxylylenediamine, paraxylylenediamine, and diaminodiphenylmethane; and polyoxyethylenediamine, polyoxypropylenediamine, triethylene glycoldiamine, and tripropylene glycoldiamine. Specifically, examples of the modification include amidation, Mannichization, and epoxy adductation.

[0034] The aqueous acrylic resin that can be applied to layer x is preferably one in which an acrylic resin is emulsion-dispersed in an aqueous medium. The acrylic resin can be a copolymer of polymerizable unsaturated monomers containing an alkyl (meth)acrylate compound. Methods for emulsion dispersion include dispersing the acrylic resin in an aqueous medium in the presence of an emulsifying component, and emulsion polymerization of a polymerizable unsaturated monomer containing an alkyl (meth)acrylate compound in the presence of water and an emulsifying component.

[0035] Examples of the alkyl (meth)acrylate compounds include alkyl (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate.

[0036] Note that "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid. Also, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylamide" means acrylamide or methacrylamide.

[0037] Furthermore, other polymerizable unsaturated monomers copolymerized with the alkyl (meth)acrylate compounds include, specifically, alkoxyalkyl (meth)acrylate compounds such as 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate; alkyl (meth)acrylate compounds such as ethylene glycol monomethyl (meth)acrylate, a polyoxyethylene chain with an alkoxy group at one end, a polyoxypropylene chain with an alkoxy group at one end, and propylene glycol monomethyl (meth)acrylate; Examples include hydroxyalkyl (meth)acrylate compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ε-caprolactone modified monoesters of (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms, and (meth)acrylate having a polyoxyethylene chain with a hydroxyl group at the molecular end; vinyl compounds such as styrene, vinyltoluene, allyl alcohol, α-methylstyrene, vinyl propionate, and vinyl acetate; and polymerizable unsaturated compounds containing carboxyl groups such as (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, and β-carboxyethyl (meth)acrylate.

[0038] Examples of the water-based sealer that can be applied to layer x include SK Water-Based EL Coat (SK Kaken), Jolieace A (Aica Kogyo), Silvia WA-100 (Nippon Tokushu Toryo), Jolieace E (Aica Kogyo), and Water-Based Elastic Surf Epoxy (SK Kaken).

[0039] A styrene-acrylic copolymer emulsion is particularly preferred as the aqueous sealer that can be applied to layer x. Specifically, the (meth)acrylates used as components of the styrene-acrylic copolymer include methyl (meth)acrylate, ethyl (meth)acrylate, i-propyl (meth)acrylate, allyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-amyl (meth)acrylate, i-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-tridecyl (meth)acrylate, n-stearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, and methyl (meth)acrylate. Cyclohexyl acid, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, adamantyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, octafluoropentyl methacrylate, pentadecafluorooctyl methacrylate, heptadecafluorodecyl methacrylate, N,Examples include polyalkylene oxide group-containing (meth)acrylic monomers such as N-dimethyl(meth)acrylamide, acryloylmorpholine, (meth)acrylonitrile, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polypropylene glycol-polybutylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, butoxypolyethylene glycol (meth)acrylate, octoxypolyethylene glycol (meth)acrylate, lauroxypolyethylene glycol (meth)acrylate, stearoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth)acrylate. These can be used individually or in combination of two or more.

[0040] Examples of styrene compounds used as constituent components of the styrene-acrylic copolymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, styrene dimer, styrene trimer, p-dimethylsilylthroxystyrene, p-tert-butyldimethylsiloxystyrene, and p-tert-butylstyrene. These are polymerizable compounds having a styrene skeleton. One type of styrene or two or more types may be used. Among these, styrene is preferred, and when two or more types of styrene are used, it is preferable to use styrene as the main component, such as by making styrene the largest mass proportion of all styrenes.

[0041] The styrene-acrylic copolymer may have other constituent components, and specific examples of such components include (meth)acrylic acid.

[0042] In the styrene-acrylic copolymer, the proportion of styrenes is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. In the styrene-acrylic copolymer, the proportion of styrenes is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0043] Furthermore, in the styrene-acrylic copolymer, the proportion of (meth)acrylate is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass. In the styrene-acrylic copolymer, the proportion of (meth)acrylate is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less.

[0044] If the styrene-acrylic copolymer contains other known polymerizable compounds besides the styrenes, the (meth)acrylate, and the (meth)acrylic acid, the proportion of the other polymerizable compounds in the styrene-acrylic copolymer is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0045] Examples of the styrene-acrylic copolymer emulsion include Boncoat (DIC), Ultrasealer III (Nippon Paint), U-Primer G (MU Matex), and others.

[0046] The amount of aqueous resin contained in the aqueous sealer that can be applied to layer x is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, in terms of solid content, per 100 parts by mass of the aqueous sealer. The amount of aqueous resin contained in the aqueous sealer is preferably 75 parts by mass or less, and more preferably 60 parts by mass or less, in terms of solid content, per 100 parts by mass of the aqueous sealer.

[0047] The amount of styrene-acrylic copolymer contained in the styrene-acrylic copolymer emulsion is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, in terms of solid content, per 100 parts by mass of the styrene-acrylic copolymer emulsion. The amount of styrene-acrylic copolymer contained in the styrene-acrylic copolymer emulsion is preferably 75 parts by mass or less, and more preferably 60 parts by mass or less, in terms of solid content, per 100 parts by mass of the styrene-acrylic copolymer emulsion.

[0048] The amount of the aqueous sealer or styrene-acrylic copolymer emulsion applied is not particularly limited, as long as it is sufficient to penetrate the inorganic substrate, but is 10 g / m². 2 The above is preferable, 50g / m 2 More preferably, 100g / m 2 The above is even more preferable. The amount of the penetrating primer to be applied is 1000 g / m². 2 The following is preferable: 800g / m 2 The following are preferable.

[0049] The layer a of the present invention comprises cement and a cationic resin, and can be provided on the layer x or directly on an inorganic substrate.

[0050] Examples of cements included in layer a include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, moderate-heat Portland cement, sulfate-resistant Portland cement, white Portland cement, alumina cement, ultrafast-setting cement, expansive cement, acidic phosphate cement, silica cement, blast furnace cement, fly ash cement, and Keens cement.

[0051] The cationic resin contained in layer a is not particularly limited as long as it is a polymer having a tertiary ammonium group or a quaternary ammonium group in its molecule. Specifically, examples include quaternary ammonium salt derivatives of polyethyleneimine, acrylic or methacrylic acid ester copolymers containing a quaternary ammonium group as a copolymer monomer, and styrene copolymers having a quaternary ammonium group.

[0052] More specifically, cationic resins include poly(diallyldimethylammonium chloride), polyethyleneimine hydrochloride, poly(2-acrylooxyethyldimethylsulfonium chloride), poly(N-methyl-4-vinylpyridium chloride), poly(2-methacryloyloxyethyltrimethylammonium chloride), and poly(4-trimethylammonium methylstyrene chloride), among which cationic (meth)acrylic acid ester copolymers and cationic styrene-butadiene rubber are particularly preferred.

[0053] Layer a may contain, if necessary, powder components such as aggregates and fillers, and / or polymers for cement admixture. Specifically, the aforementioned powder components include aggregates such as silica sand, crushed stone, perlite, vermiculite, styrene foam, ethylene vinyl acetate foam, and vinyl chloride foam, as well as fillers such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth.

[0054] Examples of cement admixture polymers that may be included in layer a include aqueous polymer dispersions, re-emulsifiable powder resins, and liquid polymers. Examples of aqueous polymer dispersions used as cement admixtures include rubber latex such as natural rubber latex, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl-butadiene methacrylate rubber, and synthetic rubber latex such as butadiene rubber; thermoplastic resin emulsions such as polyacrylic acid esters, polyvinyl acetate, polypropionate vinyl, vinylidene chloride, ethylene vinyl acetate, and polypropylene; thermosetting emulsions such as epoxy resins; resin emulsions such as asphalt, rubber asphalt, and paraffin emulsions; and mixed dispersions such as mixed latex and mixed emulsions.

[0055] Examples of the re-emulsifiable powder resin (powder emulsion) used as a cement admixture polymer in layer a include ethylene vinyl acetate resin, vinyl acetate / vinyl versate resin, vinyl acetate / vinyl versate / acrylic resin, and the like. Examples of liquid polymers used as cement admixtures include unsaturated polyester resins and epoxy resins.

[0056] The ratio of solid content of the cement and the cationic resin in layer a is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and particularly preferably 60 parts by mass or more, of the cationic resin per 100 parts by mass of cement. The ratio of solid content of the cement and the cationic resin in layer a is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 120 parts by mass or less, and particularly preferably 110 parts by mass or less, of the cationic resin per 100 parts by mass of cement.

[0057] The mixing ratio of the cement and the solid content of the powder component in layer a is preferably such that the solid content of the powder component is 0 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass or more, per 100 parts by mass of cement. The mixing ratio of the cement and the solid content of the powder component in layer a is preferably such that the solid content of the powder component is 600 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 400 parts by mass or less, and particularly preferably 300 parts by mass or less, per 100 parts by mass of cement.

[0058] Examples of the layer a (i.e., cationic substrate preparation material) containing the cement and the cationic resin include NS Cation One (Nippon Chemical Industries), Mirac Cation Filler (registered trademark) (SK Chemical Industries), Cation Tight (Yabuhara Sangyo), 1-Material Cation Filler (Nippon Paint), Dia (registered trademark) Cation Filler (Sika Japan), and the like.

[0059] Layer a can be obtained by treating the inorganic substrate with a dispersion obtained by diluting the cement and the cationic resin with water, and then drying it. The mixing ratio of cement to water in the dispersion is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more, per 100 parts by mass of cement. The mixing ratio of cement to water in the dispersion is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and particularly preferably 120 parts by mass or less, per 100 parts by mass of cement.

[0060] The method for producing the dispersion is not particularly limited, but a preferred method involves thoroughly stirring a portion of the water containing the cationic resin to form an emulsion, and then adding cement and water to form the dispersion.

[0061] Layer a may optionally contain, as other components, other resins, pigments, thickeners, rust inhibitors, dispersants, defoamers, leveling agents, anti-sedimentation agents, anti-sagging agents, curing accelerators, algaecides, fungicides, preservatives, ultraviolet absorbers, light stabilizers and the like, as necessary.

[0062] The method for treating an inorganic base material with said dispersion obtained by diluting said cement and said cationic resin with water is not particularly limited, and examples thereof include spray coating, roller coating, brush coating, trowel coating, spatula coating and the like. When the inorganic base material is concrete, it is preferable to perform the treatment after approximately 25 days have elapsed since placing, when the moisture content has become 5% or less. In order to remove dirt, adhered substances and a fragile surface layer on the dry surface, it is preferable to remove such substances by shot blasting, sandpaper or the like, clean the surface by polishing, and then perform the treatment.

[0063] The coating amount (dry) of said dispersion obtained by diluting said cement and said cationic resin with water is not particularly limited, but is 10 g / m 2 or more is preferable, and 50 g / m 2 or more is more preferable, and 100 g / m 2 or more is even more preferable. The coating amount of said dispersion is 1000 g / m 2 or less is preferable, and 800 g / m 2 or less is more preferable.

[0064] Layer b contains at least one resin selected from the group consisting of moisture-curable urethane resins, water-based acrylic resins, and water-based epoxy resins, and is a layer provided on said layer a.

[0065] The moisture-curable urethane resin that can be contained in layer b contains an isocyanate group-containing urethane prepolymer, and the isocyanate groups react with moisture (humidity) to crosslink and cure. The isocyanate group-containing urethane prepolymer can be obtained by reacting a polyol and a polyisocyanate under conditions in which the isocyanate groups of the polyisocyanate are in excess of the hydroxyl groups of the polyol (a reaction catalyst can be used if necessary), and the urethane prepolymer has isocyanate groups at its ends.

[0066] Specifically, the aforementioned polyisocyanates include aliphatic, aromatic, and aromatic aliphatic polyisocyanates. More specifically, examples include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis(isocyanate-methyl)cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate, and modified forms of these polyisocyanates. Specifically, examples of the aforementioned modified forms include biuret modified forms, isocyanurate modified forms, adduct modified forms (e.g., trimethylolpropane adducts), allophanate modified forms, uretdione modified forms, and carbodiimide modified forms. Among these, various modified forms of hexamethylene diisocyanate and various modified forms of isophorone diisocyanate are preferred from the viewpoint of curability and weather resistance. The polyisocyanates can be used individually or in combination of two or more types. Furthermore, the isocyanate group-containing urethane prepolymer can be used as the polyisocyanate.

[0067] Examples of the aforementioned polyols include acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and polycarbonate polyols.

[0068] The acrylic polyol is obtained by copolymerizing a hydroxyl group-containing (meth)acrylic acid ester with a compound having a polymerizable unsaturated group. Specific examples of the hydroxyl group-containing (meth)acrylic acid ester include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of compounds having the polymerizable unsaturated group include styrene, vinyltoluene, (meth)acrylic acid, fumaric acid, maleic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylonitrile. These compounds having the polymerizable unsaturated group can be used alone or in combination of two or more.

[0069] Note that (meth)acrylic acid refers to methylic acid or acrylic acid, (meth)acrylate refers to methacrylate or acrylate, (meth)acrylamide refers to methacrylamide or acrylamide, and (meth)acrylonitrile refers to methacrylonitrile or acrylonitrile.

[0070] The polyester polyol is obtained by a dehydration condensation reaction of a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, or pentaerythritol with a polybasic carboxylic acid such as phthalic acid, maleic acid, trimellitic acid, adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid, or suberic acid. Alternatively, the polyol may contain hydroxyl group-containing fatty acid esters obtained by decomposing natural oils such as soybean oil, linseed oil, rice bran oil, cottonseed oil, tung oil, castor oil, or coconut oil with the above-mentioned polyhydric alcohols, as all or part of the polyhydric alcohol.

[0071] The polyurethane polyol is obtained by reacting the polyhydric alcohol with the polyisocyanate under conditions of excess polyhydric alcohol. The hydroxyl group-containing fatty acid ester may also be included as all or part of the polyhydric alcohol.

[0072] The polyether polyol is obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to the polyhydric alcohol or the hydroxyl group-containing fatty acid ester.

[0073] The polycarbonate polyol can be obtained, for example, by a condensation reaction between the polyhydric alcohol, the hydroxyl group-containing fatty acid ester, and a carbonate ester such as diethyl carbonate. Furthermore, the polyhydric alcohol can also be used as the polyol. The polyols can be used alone or in combination of two or more types.

[0074] The number-average molecular weight of the polyol is preferably 500 or more, more preferably 1000 or more. Furthermore, the number-average molecular weight of the polyol is preferably 10000 or less, more preferably 5000 or less, and even more preferably 3000 or less. Furthermore, as the reaction catalyst, for example, an organometallic compound such as zirconium 2-ethylhexanoate can be used.

[0075] Examples of the aforementioned moisture-curing urethane resins include Chichibu NI Primer (Chichibu Cement), Prooflon Primer U (Nippon Special Paint), Saracene P (AGC Polymer Building Materials), and PM Primer (AGC Polymer Building Materials).

[0076] The aqueous acrylic resin that may be included in layer b represents an aqueous acrylic emulsion or a water-soluble acrylic resin.

[0077] The aqueous acrylic resin is a resin containing (meth)acrylate units, and examples include polymers or copolymers of acrylic monomers such as alkyl (meth)acrylic esters, (meth)acrylic acid, and (meth)acrylamide, or copolymers of the acrylic monomer with monomers such as styrene and maleic anhydride. The acrylic monomer may have functional groups such as hydroxyl groups, carboxyl groups, and glycidyl groups.

[0078] Examples of the acrylic monomer include acrylic acid esters and methacrylic acid esters. Specifically, examples of the acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and glycidyl acrylate.

[0079] Examples of the aforementioned methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and glycidyl methacrylate.

[0080] Examples of acrylic monomers include acrylic acid and methacrylic acid. Examples of monomers copolymerizable with the acrylic monomers include carboxylic acid-containing monomers such as crotonic acid, maleic acid, fumaric acid, and itaconic acid, their anhydrides, or half-esters.

[0081] Among the acrylic monomers mentioned above, methyl acrylate, ethyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, maleic acid, and itaconic acid are particularly preferred.

[0082] Furthermore, specific examples of styrene monomers constituting styrene-acrylic resin include styrene, α-methylstyrene, and β-methylstyrene. Among these styrene monomers, α-methylstyrene is particularly preferred.

[0083] The aqueous acrylic emulsion is preferably a styrene-acrylic resin or an emulsion containing an acrylic resin. More preferably, it is an emulsion containing a styrene-acrylic resin. The acrylic monomers constituting the acrylic resin are the same as those described above.

[0084] An emulsion is a form in which a resin, which is insoluble or sparingly soluble in water, is dispersed into small particles and stabilized. Another example of an emulsion is a copolymer emulsion obtained by copolymerizing the monomer using a water-soluble acrylic resin as a polymer emulsifier.

[0085] The average particle size of the aqueous acrylic emulsion is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more. The average particle size of the aqueous acrylic emulsion is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 250 nm or less. The average particle size can be measured, for example, as the D50 value by dynamic light scattering.

[0086] Furthermore, the weight-average molecular weight of the acrylic resin in the aqueous acrylic emulsion is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. The weight-average molecular weight of the acrylic resin in the aqueous acrylic emulsion is preferably 2,000,000 or less, more preferably 1,500,000 or less, and even more preferably 100,000.

[0087] The water-soluble acrylic resin is preferably an acrylic resin such as a styrene-acrylic resin having hydrophilic groups such as carboxyl groups. Furthermore, the water-soluble acrylic resin is preferably a water-soluble resin in which the hydrophilic groups are solubilized with an amine compound or a basic compound such as an alkali metal.

[0088] Examples of the amine compound include ammonia, alkylamines such as diethylamine, triethylamine, and ethylenediamine, and alkanolamines such as monoethanolamine, ethylethanolamine, diethylethanolamine, diethanolamine, and triethanolamine. Examples of the alkali metal include sodium hydroxide and potassium hydroxide.

[0089] The acid value of the water-soluble acrylic resin is preferably 150 mg KOH / g or higher, and more preferably 180 mg KOH / g or higher. The acid value of the water-soluble acrylic resin is preferably 300 mg KOH / g or lower, and more preferably 260 mg KOH / g. The weight-average molecular weight of the water-soluble acrylic resin is preferably 1,500 or more, and more preferably 4,000 or more. The weight-average molecular weight of the water-soluble acrylic resin is preferably 60,000 or less, and more preferably 30,000 or less.

[0090] Examples of the aforementioned water-based acrylic resins include TMR Primer (Nippon Special Paint), Floor Top Aqua (Atomix), and SF Under (SK Kaken).

[0091] Specific examples of aqueous epoxy resins that may be included in layer b include aqueous dispersions obtained by graft polymerization of a fatty acid (for example, a carboxyl group-containing vinyl monomer) onto an epoxy resin and then neutralizing it.

[0092] Specifically, the epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD ​​type epoxy resin; epoxy ester resins obtained by modifying the bisphenol type epoxy resin with a dibasic acid, etc.; novolac type epoxy resins such as cresol novolac type epoxy resin and phenol novolac type epoxy resin; alicyclic epoxy resins; polyglycol type epoxy resins; hydrogenated bisphenol A type epoxy resin; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether Examples include aliphatic epoxy resins such as ricidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalate diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, and polyglycerin polyglycidyl ether, as well as epoxy group-containing acrylic resins composed of epoxy group-containing acrylic monomers such as glycidyl (meth)acrylate. These can be used individually or in combination of two or more types.

[0093] Specifically, the aqueous epoxy resin mentioned above includes an emulsion obtained by forcibly emulsifying a bisphenol-type epoxy resin with an emulsifier. Furthermore, specific examples of the aqueous epoxy resin include alkyl types obtained by adding epichlorohydrin to polyols such as sorbitol, pentaerythritol, and glycerin. The aqueous epoxy resin may be modified, and specific examples include acrylic-modified, urethane-modified, amine-modified, and ester-modified epoxy resins.

[0094] Examples of the aforementioned water-based epoxy resins include Ode High Pump Primer (Nippon Paint), Water-Based High Pump Primer (Nippon Paint), Yukacrete (Daido Paint), Atom Water-Based Epoxy Primer (Atomix), One Two Water-Breathable ECO (Suzuka Fine), Water-Based Cooltect Primer (SK Kaken), Water-Based Hybrid Sealer (SK Kaken), and others.

[0095] The aforementioned layer b may contain, as necessary, other components such as other resins, pigments, thickeners, rust inhibitors, dispersants, defoamers, leveling agents, settling inhibitors, anti-sagging agents, curing accelerators, anti-algal agents, anti-fungal agents, preservatives, ultraviolet absorbers, light stabilizers, etc.

[0096] The method for producing the layer b is not particularly limited, and specifically, a composition 1 containing at least one resin selected from the group consisting of moisture-curing urethane resins, aqueous acrylic resins, and aqueous epoxy resins may be used for spray painting, roller painting, brush painting, trowel painting, spatula painting, etc.

[0097] The composition 1 containing the resin may be a homogeneous solution, emulsion, or dispersion, using water or an organic solvent as the solvent. The proportion of resin solid components in the composition 1 is preferably 1% by mass or more and 60% by mass or less, depending on the manufacturing method.

[0098] The coating amount (DRY) of composition 1 containing the resin is 5 g / m². 2 Preferably, 10 g / m 2 The above is more preferable. The coating amount (DRY) of the resin composition 1 is 50 g / m². 2 The following is preferable: 30 g / m 2 The following are preferable.

[0099] The layer s comprises an adhesive layer or a tack layer and a functional layer having a predetermined functionality. The resin used in the adhesive or tack layer is a known resin for adhesive or tack layers. Examples of functional layers include radiative cooling and / or heat shielding functions.

[0100] In this embodiment, the manufacturing method preferably involves treating the inorganic substrate with the aqueous sealer or the styrene-acrylic copolymer emulsion to form a layer x (step X), then forming a layer a containing cement and a cationic resin on layer x (step A), then forming at least one layer b selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin on layer a (step B), and then curing until the solvents are sufficiently removed and curing has progressed sufficiently to form a layer s comprising an adhesive layer or tack layer and a film or sheet (step C).

[0101] This method allows for the easy and reliable attachment of a film or sheet having an adhesive or tack layer to layer b via the adhesive or tack layer. Furthermore, this method ensures that the film or sheet having the adhesive or tack layer is firmly attached to an inorganic substrate and that the attachment is maintained.

[0102] The manufacturing method of the present invention more preferably includes one or more steps Y for reforming layer b between steps B and C.

[0103] The at least one resin selected from the group consisting of moisture-curing urethane resins, aqueous acrylic resins, and aqueous epoxy resins included in the reformed layer b is, specifically, the same as those exemplified as the at least one resin selected from the group consisting of moisture-curing urethane resins, aqueous acrylic resins, and aqueous epoxy resins included in layer b. The initially formed layer b (hereinafter referred to as "layer b1") and the reformed layer b (hereinafter referred to as "layer b2") may be the same or different. By repeating process Y multiple times, the adhesion of layer s to the slate material becomes more reliable and stronger.

[0104] Since films or sheets having the aforementioned adhesive or tack layer are usually attached and fixed to smooth surfaces, it is extremely difficult to attach them to surfaces that are not smooth, such as inorganic substrates. However, the manufacturing method of the present invention makes this easy and reliable.

[0105] Furthermore, by using the manufacturing method of the present invention, functionality can be easily imparted to existing structures made of inorganic substrates, and the adhesion can be stably maintained. For example, by attaching the film having radiative cooling and / or heat-shielding function to a corrugated roof made of slate material using the method of the present invention, the temperature inside the corrugated roof can be sufficiently lowered to the outside temperature. In addition, by being able to stably attach the functional film, the suppression of temperature rise inside the building can be stably maintained.

[0106] Furthermore, since the present invention allows for the implementation of each step of the invention while omitting or minimizing the step of smoothing the surface of the inorganic substrate, it has the advantageous effect of avoiding the scattering of asbestos during the surface smoothing step of the inorganic substrate. In addition, since the present invention makes it possible to attach various functional sheet materials having an adhesive layer to the inorganic substrate, it is possible to prevent deterioration of the inorganic substrate itself or to reinforce the inorganic substrate with the sheet material. This, in turn, has the effect of extending the lifespan of slate roofs that require asbestos countermeasures or delaying the timing of renovations.

[0107] Furthermore, according to the present invention, water-based substances can be selected to avoid using flammable adhesives such as glue in each step. Therefore, it has the advantageous effect of being suitably applied even to structures such as hazardous materials warehouses where flammable materials cannot be used. In addition, in hazardous materials warehouses and the like, it has been difficult to suppress the rise in internal temperature because air conditioners that use gas cannot be installed. However, according to the present invention, it is possible to effectively prevent the rise in temperature of structures and buildings where air conditioners and other air conditioning units cannot be used, keep the temperature inside the warehouse as low as possible, and greatly contribute to preventing heatstroke among workers inside. Moreover, since the work process of the present invention is very simple and easy, it has the advantage of making it easy to carry out sheet material installation work.

[0108] In the above embodiment, a more preferable example was shown in which layer x is formed on an inorganic substrate before forming layer a, etc., but step X can be omitted. [Examples]

[0109] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited to these examples. Furthermore, unless otherwise specified in this specification, the units of measurement and measurement methods shall conform to the provisions of JIS (Japanese Industrial Standards).

[0110] The materials constituting the laminate of the present invention are as follows: Layer a: Cationic primer A Layer b1: Moisture-curing urethane resin primer B1, Water-based acrylic resin primer B2, or Water-based epoxy resin primer B3 Layer b2: Moisture-curing urethane resin primer B1, Water-based acrylic resin primer B2, or Water-based epoxy resin primer B3 Layer x: Water-based sealer C1, or Styrene-acrylic copolymer emulsion C2 [Examples]

[0111] A cationic primer A was applied to the concrete block with a roller, either in the amount recommended for a commercially available product (hereinafter referred to as the "standard application amount") or less than the standard application amount, and then dried to form layer a. On layer a, water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b1. A layer s was formed by attaching a SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) to layer b1 via an adhesive layer, thereby obtaining a laminate 1. Three days after the film was applied, it remained firmly attached to the concrete block and could not be easily removed unless someone tried to peel it off. [Examples]

[0112] A cationic primer A was applied to the concrete block using a roller in a standard application amount or less, and then allowed to dry to form layer a. On layer a, a water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b1. On layer b1, water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b2. A SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) was attached to layer b2 via an adhesive layer to form layer s, thereby obtaining laminate 2. Three days after the film was applied, an attempt was made to peel it off the concrete block, but it was difficult to remove because it was firmly attached. When it was peeled off, the very surface layer of the concrete block partially peeled off along with layers a, b1, and b2. [Examples]

[0113] Water-based sealer C1 was applied to the concrete block using a roller in the standard application amount or more, and allowed to dry to form layer x. On layer x, a cationic primer A was applied with a roller in a standard application amount or less than the standard application amount, and allowed to dry to form layer a. On layer a, water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b1. A layer s was formed by attaching a SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) to layer b1 via an adhesive layer, thereby obtaining a laminate 3. Three days after the film was applied, an attempt was made to peel it off the concrete block, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the very surface layer of the concrete block, along with layers a and b1, partially peeled off. [Examples]

[0114] Water-based sealer C1 was applied to the concrete block using a roller in the standard application amount or more, and allowed to dry to form layer x. On layer x, a cationic primer A was applied with a roller in a standard application amount or less than the standard application amount, and allowed to dry to form layer a. On layer a, water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b1. On layer b1, water-based epoxy resin primer B3 was applied with a roller in a standard application amount or less, and allowed to dry to form layer b2. A SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) was attached to layer b2 via an adhesive layer to form layer s, thereby obtaining a laminate 4. Three days after the film was applied, an attempt was made to peel it off the concrete block, but it was extremely difficult to remove because it was adhered very firmly. When it was finally removed, the very surface layer of the concrete block peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0115] A styrene-acrylic copolymer emulsion C2 was applied to a concrete block in a standard application amount or more, and then dried to form layer x. On layer x, a cationic primer A was applied in a standard amount or less than the standard amount, and allowed to dry to form layer a. A water-based epoxy resin primer B3 was applied to layer a in a standard application amount or less, and allowed to dry to form layer b1. A layer s was formed by attaching a SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) to layer b1 via an adhesive layer, thereby obtaining a laminate 5. Three days after the film was applied, an attempt was made to peel it off the concrete block, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the very surface layer of the concrete block, along with layers a and b1, partially peeled off. [Examples]

[0116] A styrene-acrylic copolymer emulsion C2 was applied to a concrete block in a standard application amount or more, and then dried to form layer x. On layer x, a cationic primer A was applied in a standard amount or less than the standard amount, and allowed to dry to form layer a. A water-based epoxy resin primer B3 was applied to layer a in a standard application amount or less, and allowed to dry to form layer b1. A water-based epoxy resin primer B3 was applied to layer b1 in a standard or lesser amount and allowed to dry to form layer b2. A SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) was attached to layer b2 via an adhesive layer to form layer s, thereby obtaining a laminate 6. Three days after the film was applied, an attempt was made to peel it off the concrete block, but it was extremely difficult to remove because it was adhered very firmly. When it was finally removed, the very surface layer of the concrete block peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0117] A water-based sealer C1 was applied to the slate in a standard or larger amount, and allowed to dry to form layer x. On layer x, a cationic primer A was applied in a standard amount or less than the standard amount, and allowed to dry to form layer a. On layer a, moisture-curing urethane resin primer B1 was applied in a standard amount or less than the standard amount, and allowed to dry to form layer b1. A layer s was formed by attaching a SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) to layer b1 via an adhesive layer, thereby obtaining a laminate 7. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off. [Examples]

[0118] A water-based sealer C1 was applied to the slate in a standard or larger amount, and allowed to dry to form layer x. On layer x, a cationic primer A was applied in a standard amount or less than the standard amount, and allowed to dry to form layer a. On layer a, moisture-curing urethane resin primer B1 was applied in a standard amount or less than the standard amount, and allowed to dry to form layer b1. On layer b1, moisture-curing urethane resin primer B1 was applied in a standard amount or less than the standard amount, and allowed to dry to form layer b2. A SPACECOOL® film (SCF-A25M-XNW, manufactured by SPACECOOL Inc.) was attached to layer b2 via an adhesive layer to form layer s, thereby obtaining a laminate 8. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the surface layer of the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0119] A laminate 9 was obtained in the same manner as in Example 7, except that a water-based epoxy resin primer B3 was applied in the standard amount or less than the standard amount instead of the moisture-curing urethane resin primer B1. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off. [Examples]

[0120] A laminate 10 was obtained in the same manner as in Example 8, except that a water-based epoxy resin primer B3 was applied in a standard or lesser amount than the standard amount instead of the moisture-curing urethane resin primer B1. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the surface layer of the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0121] A laminate 11 was obtained in the same manner as in Example 7, except that a water-based acrylic resin primer B2 was applied in a standard or lesser amount than the standard amount instead of the moisture-curing urethane resin primer B1. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off. [Examples]

[0122] A laminate 12 was obtained in the same manner as in Example 8, except that instead of moisture-curing urethane resin primer B1, water-based acrylic resin primer B2 was applied with a roller in a standard or lesser amount. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the surface layer of the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0123] A laminate 13 was obtained in the same manner as in Example 7, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off. [Examples]

[0124] A laminate 14 was obtained in the same manner as in Example 8, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0125] A laminate 15 was obtained in the same manner as in Example 9, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0126] A laminate 16 was obtained in the same manner as in Example 10, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, when we attempted to peel it off the slate, it was extremely difficult to remove because it was very firmly attached. When we finally managed to peel it off, the slate peeled off over a wide area along with layers a, b1, and b2. [Examples]

[0127] A laminate 15 was obtained in the same manner as in Example 11, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off. [Examples]

[0128] A laminate 18 was obtained in the same manner as in Example 12, except that instead of the aqueous sealer C1, a styrene-acrylic copolymer emulsion C2 was applied in a standard or larger amount. Three days after the film was applied, an attempt was made to peel it off the slate, but it was difficult to remove because it was adhered relatively firmly. When it was peeled off, the surface layer of the slate, along with layers a and b1, partially peeled off.

[0129] [Comparative Example 1] We attempted to directly attach and fix a film similar to the one used in Example 7 to a slate similar to the one in Example 7, but we were unable to securely attach it, and the sheet peeled off easily. [Industrial applicability]

[0130] The present invention's method for manufacturing laminates allows for the addition of various functions to structures made of concrete or the like simply by attaching them to existing films, making it useful in the construction industry.

Claims

1. Step A involves forming a layer a containing cement and cationic resin on an inorganic substrate, Step B involves forming a layer b on the aforementioned layer a, which contains at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin. A method for manufacturing a laminate, comprising step C of attaching a layer s comprising an adhesive layer or a sticky layer and a film or sheet onto the layer b via the adhesive layer or the sticky layer.

2. Step X involves applying an aqueous sealer or styrene-acrylic copolymer emulsion to an inorganic substrate to form a layer x, Step A involves forming a layer a containing cement and a cationic resin, Step B involves forming a layer b on the aforementioned layer a, which contains at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin. A method for manufacturing a laminate, comprising step C of attaching a layer s comprising an adhesive layer or a sticky layer and a film or sheet onto the layer b via the adhesive layer or the sticky layer.

3. A method for manufacturing a laminate according to claim 1 or 2, further comprising one or more steps Y between step B and step C, in which step Y is performed to further form the layer b containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin.

4. The method for producing a laminate according to claim 1 or 2, wherein the cationic resin is a cationic acrylic copolymer or a cationic styrene-butadiene rubber.

5. The method for manufacturing a laminate according to claim 1 or 2, wherein the inorganic substrate is a substrate containing at least one of cement, mortar, or slate.

6. The method for manufacturing a laminate according to claim 1 or 2, wherein the layer s is a functional layer having a radiative cooling function and / or a heat shielding function.

7. A laminate comprising an inorganic substrate, a layer a containing cement and a cationic resin, a layer b containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin, and a layer s comprising an adhesive layer or tack layer and a functional layer having radiative cooling and / or heat-shielding functions, in this order.

8. A laminate comprising an inorganic substrate, a layer x obtained by applying and drying an aqueous sealer or aqueous styrene-acrylic copolymer emulsion, a layer a containing cement and a cationic resin, a layer b containing at least one resin selected from the group consisting of moisture-curing urethane resin, aqueous acrylic resin, and aqueous epoxy resin, and a layer s comprising an adhesive layer or tack layer and a functional layer having radiative cooling and / or heat-shielding functions, in this order.

9. The laminate according to claim 7 or 8, wherein the inorganic substrate is a substrate containing at least one of cement, mortar, or slate.

10. The laminate according to claim 7 or 8, wherein the cationic resin is a cationic acrylic copolymer or a cationic styrene-butadiene rubber.

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