JP6324236B2 - Concrete surface coating method - Google Patents

Description

  The present invention relates to a concrete surface coating method, and more specifically, a protective film for protecting a concrete surface from scratches and a coating film excellent in surface smoothness for smoothing the concrete surface and improving design properties. The present invention relates to a concrete surface covering method formed on a concrete surface.

  The surface of concrete, such as lightweight cellular concrete (ALC), is painted to protect the base material, prevent performance degradation due to water intrusion, and neutralize due to carbon dioxide intrusion. Thus, a coating film is formed. In particular, lightweight cellular concrete is usually boarded in a manufacturing plant and brought to a construction site, and this is laid on a framework to form a building, and then the outer wall surface is painted. is there. Such lightweight cellular concrete board has a foamed structure, so damage such as chipping is likely to occur during transportation. Also, during transportation and construction, dust from fine cracks and chips, etc., drops due to the foamed structure. There are various problems, such as being easy to make and it is difficult to impart designability due to the unevenness of the foam structure on the surface.

  When forming a coating film on the surface of such concrete, especially a lightweight cellular concrete board, a coating method is often employed. As for painting, it is common to apply coating materials repeatedly such as “undercoating”, “intermediate coating”, and “overcoating”, and these coating materials are often dispersed or diluted in a liquid. When applied to the surface of concrete, especially lightweight cellular concrete board, the liquid component is often dried repeatedly.

  However, when the liquid component forming the coating material is an organic solvent, there are concerns about odor problems and adverse effects on the human body, and exposure of the organic solvent due to overcoating has become a work problem. In order to improve this problem, a method of replacing the liquid component with water by using an emulsification technique is now quite popular. However, in this case as well, since it takes a considerable time to dry, a new problem arises that when the overcoating is assumed, a considerable time is required for the coating.

  As another method of coating the concrete surface to form a coating film, thermosetting resin powder mixed with siliceous raw material powder is applied to the concrete surface, and thermosetting resin powder is applied by autoclave curing. There has also been proposed a method of curing (see, for example, Patent Document 1).

JP-A-11-79869

  However, in the disclosed technique disclosed in Patent Document 1, it is necessary to apply a coating film on the concrete surface by electrostatic spraying or the like, which is inferior in productivity and workability. Furthermore, further improvements have been demanded in terms of the protection of the concrete surface and the surface smoothness for smoothing the concrete surface and improving the design.

  Therefore, an object of the present invention is to form a coating film on the surface of the concrete that is excellent in productivity and workability and further excellent in the protection and smoothness of the concrete surface under such a background.

However, as a result of intensive studies in view of such circumstances, the present inventor has found that a specific binder polymer (A) is used as the curable resin composition in forming a coating film on the concrete surface using the curable resin composition. A curable resin composition [i] comprising a reactive oligomer (B) having at least one unsaturated group, a reactive monomer (C) having at least one unsaturated group, and a polymerization initiator (D). Further, a laminated film of the layer [I] composed of the curable resin composition [i] and the support film [II] is laminated on the concrete surface, and the concrete on which the laminated film is laminated is put in a bag and packaged. By curing the curable resin composition layer [I] by heating or irradiating with active energy rays as a body, it is excellent in productivity and workability, and also in the protection of concrete surface and surface smoothness. It found that the membrane is formed, thereby completing the present invention.

That is, the gist of the present invention is a concrete surface coating method in which a coating film is formed on a concrete surface. The binder polymer (A), the reactive oligomer (B) having one or more unsaturated groups, and 1 unsaturated group. Ri Na contain reactive monomers having more pieces (C) and a polymerization initiator (D), the binder polymer (a) is (meth) acrylic resin (a1) der Ru curable resin compositions from [i] After the layer [I] and the supporting film [II] are laminated on the concrete, the curable resin composition layer [I] is brought into contact with the concrete surface. Put the curable resin composition in a bag made of a layer film or a multilayer film, and set the atmosphere of the package sealed under reduced pressure to 90 ° C or higher, or irradiate the package with active energy rays. By a concrete surface coating method characterized by forming a coating film on the concrete surface.

  The concrete surface coating method of the present invention is excellent in productivity and workability in forming a coating film on a concrete surface, and further has an effect of being excellent in the protection and smoothness of the concrete surface.

  The present invention will be described in detail below, but these show examples of desirable embodiments.

  In the concrete surface coating method of the present invention, a layered film for covering a concrete surface (hereinafter simply referred to as “laminated film”) in which a layer [I] composed of a curable resin composition [i] and a support film [II] are laminated. Also called). The curable resin composition [i] comprises a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, a reactive monomer (C) having one or more unsaturated groups, and a polymerization initiator ( D). Hereinafter, each component will be described.

<Binder polymer (A)>
The binder polymer (A) in the present invention is used for the purpose of moderate flexibility of the uncured film and suppression of surface tackiness, improvement of durability of the cured film, and adjustment of hardness. For example, (meth) acrylic Resins, polyurethane resins, epoxy resins and the like can be mentioned. Above all, the durability and hardness adjustment of the cured film in terms of facilitating (meth) acrylic resin (a1) is rather preferable, as the binder polymer (A) in the present invention (meth) acrylic resin (a1 ) Is used.
Hereinafter, the (meth) acrylic resin (a1) will be described more specifically.
Note that (meth) acryl represents acryl or methacryl, and (meth) acrylate represents acrylate or methacrylate.

[(Meth) acrylic resin (a1)]
The (meth) acrylic resin (a1) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer. (Meth) acrylic-type resin (a1) can be used individually by 1 type or in combination of 2 or more types.

The (meth) acrylic resin (a1) preferably contains the (meth) acrylic acid ester monomer (a2) as the main polymerization component, and if necessary, the functional group-containing monomer (a3) and other copolymers. The polymerizable monomer (a4) can also be used as a copolymerization component.
Examples of the (meth) acrylic acid ester monomer (a2) include, for example, aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl ester, and aromatic monomers such as (meth) acrylic acid phenyl ester. Examples include (meth) acrylic acid ester monomers.

About this (meth) acrylic acid alkyl ester, it is preferable that carbon number of an alkyl group is 1-12 normally, especially 1-8, specifically, methyl (meth) acrylate, ethyl (meth) acrylate. , N-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and the like. Examples of the (meth) acrylic acid phenyl ester include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Examples of other (meth) acrylic acid ester monomers (a2) include tetrahydrofurfuryl (meth) acrylate. These can be used alone or in combination of two or more.

  Among these (meth) acrylic acid ester monomers (a2), methyl (meth) acrylate, n-butyl (meth) acrylate, 2 in terms of copolymerizability, adhesive physical properties, ease of handling, and availability of raw materials. -Ethylhexyl (meth) acrylate is preferably used.

  Examples of the functional group-containing monomer (a3) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group-containing monomer, a phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, other nitrogen-containing monomers, and a glycidyl group-containing Monomers, phosphoric acid group-containing monomers, sulfonic acid group-containing monomers and the like can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate, etc. Monomers containing primary hydroxyl groups such as caprolactone-modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 -Secondary hydroxyl group-containing monomers such as phenoxypropyl (meth) acrylate; tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.

  Examples of the hydroxyl group-containing monomer include polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol-mono (meta). ) Oxyalkylene-modified monomers such as acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.

  Examples of the carboxyl group-containing monomer include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. (Eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyloxyethyl) Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahi Rofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like. Such a carboxyl group-containing monomer may be used as it is, or may be used in the form of a salt neutralized with an alkali.

  Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol. (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol Polypropylene glycol-mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearo Aliphatic (meth) acrylic acid esters such as xypolyethylene glycol mono (meth) acrylate and the like. Examples of the phenoxy group-containing monomer include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate. And acrylate esters of aromatic (meth) acrylates such as phenoxypolyethylene glycol-polypropylene glycol (meth) acrylate and nonylphenol ethylene oxide adduct (meth) acrylate.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.

Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
Examples of the nitrogen-containing monomer other than the amide group-containing monomer and the amino group-containing monomer include acryloylmorpholine.

  Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.

  Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .

  Examples of other copolymerizable monomers (a4) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, Examples include vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinylketone.

  For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate A compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.

  In the acrylic resin (a1), the content ratio of the (meth) acrylic acid ester monomer (a2), the functional group-containing monomer (a3), and the other copolymerizable monomer (a4) is (meth) acrylic acid ester monomer (A2) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, and the functional group-containing monomer (a3) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight, The other copolymerizable monomer (a4) is preferably 0 to 50% by weight, particularly preferably 5 to 40% by weight.

  The acrylic resin (a1) in the present invention is a coating film that is excellent in compatibility with a urethane (meth) acrylate compound suitable as a reactive oligomer (B) having one or more unsaturated groups. From the viewpoint of adjusting the weather resistance and hardness of the polymer, a polymer containing methyl (meth) acrylate as a polymerization component is preferable, and a polymer containing methyl methacrylate as a polymerization component is particularly preferable. Methyl methacrylate is preferred.

  In the present invention, the acrylic resin (a1) can be produced by polymerizing the monomer components (a2) to (a4). Such polymerization can be performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. For example, in an organic solvent, a polymerization monomer such as the (meth) acrylic acid ester monomer (a2), a functional group-containing monomer (a3), other copolymerizable monomer (a4), a polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.) are mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 2 to 20 hours.

  Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, n-propyl alcohol, and isopropyl alcohol. Aliphatic alcohols such as acetone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The glass transition temperature (Tg) of acrylic resin (a1) is 40-120 degreeC normally, Preferably it is 60-110 degreeC. If the glass transition temperature is too high, the amount of the acrylic resin (a1) that can be blended when preparing the curable resin composition [i] is limited, and the adjustment range of durability and flexibility of the coating film is narrowed. As a result, the durability of the coating film tends to decrease, or the strength tends to decrease because the coating film becomes too hard. If the glass transition temperature is too low, the thermal durability of the coating film tends to decrease.

The glass transition temperature (Tg) is calculated from the following Fox equation.
1 / Tg = w1 / Tg1 + w2 / Tg2 + ... Wk / Tgk
Where Tg is the glass transition temperature of the copolymer, Tg1, Tg2,... Tgk is the Tg of the homopolymer of each monomer component, w1, w2,. ... Wk represents the molar fraction of each monomer component, and w1 + w2 +... Wk = 1.

The weight average molecular weight of the acrylic resin (a1) thus obtained is usually 10,000 to 3,000,000, preferably 20,000 to 2.5 million.
In addition, said weight average molecular weight is based on standard polystyrene molecular weight conversion, column: Shodex GPC KF in high performance liquid chromatography (The product of Japan Waters, "Waters2695 (main body)" and "Waters2414 (detector)"). −806 L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm ) Can be used for measurement.

<Reactive oligomer (B) having one or more unsaturated groups>
Examples of the reactive oligomer (B) having one or more unsaturated groups in the present invention include urethane (meth) acrylate compounds (b1), epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and the like. Can be mentioned. Among these, the urethane (meth) acrylate compound (b1) is preferable from the viewpoint of imparting appropriate elasticity to the cured film.
Hereinafter, the urethane (meth) acrylate compound (b1) will be described more specifically.

[Urethane (meth) acrylate compound (b1)]
The urethane (meth) acrylate compound (b1) used in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b2), a polyvalent isocyanate compound (b3), and a polyol compound (b4). A urethane (meth) acrylate type compound (b1) is mentioned.

  The weight average molecular weight of the urethane (meth) acrylate compound (b1) used in the present invention is preferably 500 to 50000, more preferably 1000 to 30000. If the weight average molecular weight is too small, the coating film tends to be brittle, and if it is too large, the coating film becomes too hard and impact resistance tends to decrease.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (exclusion) is a high performance liquid chromatography (The Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It can be measured by using a series.

The urethane (meth) acrylate compound (b1) has a viscosity at 60 ° C. of preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and still more preferably 1,000 to 100,000 mPa. -S. When the viscosity is out of the above range, the coating property at the time of forming the coating film tends to decrease.
The viscosity can be measured with an E-type viscometer.

[Hydroxyl group-containing (meth) acrylate compound (b2)]
Examples of the hydroxyl group-containing (meth) acrylate compound (b2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable because it can alleviate curing shrinkage during coating film formation, and 2-hydroxyethyl (meta) is particularly preferable. ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like, and It is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility.
Moreover, these can be used individually by 1 type or in combination of 2 or more types.

[Polyisocyanate compound (b3)]
Examples of the polyvalent isocyanate compound (b3) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) Cycloaliphatic polyisocyanates such as hexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.).

  Among these, from the point of little yellowing, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1, An alicyclic diisocyanate such as 3-bis (isocyanatomethyl) cyclohexane is preferably used, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate is particularly preferably used in terms of low curing shrinkage, and further Preferably, isophorone diisocyanate is used in terms of excellent reactivity and versatility.

[Polyol compound (b4)]
Examples of the polyol compound (b4) include polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyol, polybutadiene polyol, (meth) acrylic polyol, polysiloxane polyol, and the like. And alkylene glycols such as propylene glycol and neopentyl glycol.

  Examples of the polyether polyol include, for example, polyether glycols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Examples include coalescence.

  Examples of the polyester-based polyol include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

  Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.

  Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).

  Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.

  The polycarbonate polyol may be a compound having a carbonate bond in the molecule and a terminal being a hydroxyl group, and may have an ester bond together with the carbonate bond.

  Examples of the polyolefin-based polyol include those having a homopolymer or copolymer such as ethylene, propylene, and butene as a saturated hydrocarbon skeleton, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

  Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.

  Examples of the polysiloxane-based polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

  Among these, polyester-based polyols and polyether-based polyols are preferable, and polyester-based polyols are particularly preferable because they are excellent in mechanical properties such as flexibility during curing.

  As a weight average molecular weight of the said polyol type compound (b4), 500-8000 are preferable, Especially preferably, it is 550-5000, More preferably, it is 600-3000. If the molecular weight of the polyol compound (b4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if too small, curing shrinkage tends to increase and stability tends to decrease.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column: Shodex GPC KF-806L (exclusion) is a high performance liquid chromatography (The Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It can be measured by using a series.

  The urethane (meth) acrylate compound (b1) is usually the above-mentioned hydroxyl group-containing (meth) acrylate compound (b2), polyvalent isocyanate compound (b3) and polyol compound (b4) in a reactor or separately. It can be manufactured by charging and reacting. Further, the reaction product obtained by reacting the polyol compound (b4) and the polyvalent isocyanate compound (b3) in advance is reacted with the hydroxyl group-containing (meth) acrylate compound (b2) to obtain urethane (meth) acrylate. The compound (b1) can also be produced, and this production method is useful in terms of reaction stability, reduction of byproducts, and the like.

  For the reaction between the polyol compound (b4) and the polyvalent isocyanate compound (b3), known reaction means can be used. In that case, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (b3) to the hydroxyl group in the polyol compound (b4) is usually about 2n: (2n-2) (n is an integer of 2 or more). By doing this, after obtaining a terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (b2) becomes possible.

  The addition reaction of the reaction product obtained by reacting the polyol compound (b4) and the polyvalent isocyanate compound (b3) in advance with the hydroxyl group-containing (meth) acrylate compound (b2) is also a known reaction. Means can be used.

  The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b2) is, for example, that the polyisocyanate compound (b3) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b2). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b2) is about 1: 2, and the polyisocyanate compound (b3) has three isocyanate groups. When the hydroxyl group-containing (meth) acrylate compound (b2) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b2) is about 1: 3.

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b2), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (b1) is obtained.

  In the reaction between the polyol compound (b4) and the polyvalent isocyanate compound (b3), and the reaction product and the hydroxyl group-containing (meth) acrylate compound (b2), a catalyst is used for the purpose of promoting the reaction. It is also preferable to use. Examples of such catalysts include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin, zinc octoate, tin octoate, cobalt naphthenate, stannous chloride, and stannic chloride. Metal salts of the following: triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl- In addition to amine-based catalysts such as 1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide and the like, organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, Bismuth ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, neo Bismuth canate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate Examples thereof include bismuth-based catalysts such as organic acid bismuth salts such as salts, among which dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are suitable.

  In the reaction between the polyol compound (b4) and the polyvalent isocyanate compound (b3), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b2), it reacts with the isocyanate group. Organic solvents having no functional group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.

  Moreover, reaction temperature is 30-90 degreeC normally, Preferably it is 40-80 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

  The urethane (meth) acrylate-based compound (b1) used in the present invention preferably has 20 or less ethylenically unsaturated groups from the viewpoint of utilizing the adhesiveness with concrete which is a structural characteristic. Particularly preferred are those having 10 or less ethylenically unsaturated groups, and more preferred are those having 5 or less ethylenically unsaturated groups.

  The content ratio (weight ratio) of the binder polymer (A) and the reactive oligomer (B) having one or more unsaturated groups is usually binder polymer (A): reactive oligomer (B) = 90: 10-10. : 90, preferably 70:30 to 20:80, particularly preferably 60:40 to 30:70. If the binder polymer (A) is too small (the reactive oligomer (B) is too much), the surface of the coating film after curing will be sticky, which will hinder subsequent processes and cure the coating film. There is a tendency that shrinkage increases and peeling occurs at the edge of the bonding surface, and when the binder polymer (A) is too much (the reactive oligomer (B) is too little), the uncured film is hard. It becomes too much, and the film is cracked by handling before bonding, and the followability at the time of bonding tends to be impaired.

<Reactive monomer (C) having one or more unsaturated groups>
As the reactive monomer (C) having one or more unsaturated groups in the present invention, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, other ethylenically unsaturated monomers, and the like can be used.

  As the monofunctional monomer, a monomer containing one ethylenically unsaturated group is used. For example, styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate Rate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified ( Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate -Furester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  As the bifunctional monomer, a monomer containing two ethylenically unsaturated groups is used. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) ) Acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, etc. .

  As the trifunctional or higher functional monomer, a monomer containing three or more ethylenically unsaturated groups is used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin Polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol pen (Meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate Etc.

  Examples of the other ethylenically unsaturated monomers include, in addition to the above, a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid Examples include acid dimers, acrylic acid trimers, methacrylic acid trimers, acrylic acid tetramers, and methacrylic acid tetramers. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyl. Examples thereof include oxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  As the reactive monomer (C) having one or more unsaturated groups in the present invention, a polyfunctional monomer of a bifunctional monomer and a trifunctional or higher monomer is preferable, and a polyfunctional (meth) acrylate compound (c1) is particularly preferable. It is.

The content of the reactive monomer (C) in the curable resin composition [i] is 1 to 100 weights when the total of the binder polymer (A) component and the reactive oligomer (B) component is 100 parts by weight. Parts, preferably 3 to 80 parts by weight, more preferably 5 to 70 parts by weight.
If the content of the reactive monomer (C) is too small, the flexibility of the coating film before pasting tends to be impaired, and the processability tends to be remarkably impaired. There is a tendency for impact properties to decrease and become brittle.

<Polymerization initiator (D)>
Examples of the polymerization initiator (D) in the present invention include a thermal polymerization initiator and a photopolymerization initiator.
The thermal polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis2,4 -Dimethylvaleronitrile, dimethyl-2,2'-azobisisoobylate, 1,1'-azobis (cyclohexane-1-carbonitrile), 1,1'-azobis (1-acetoxy1-phenylethane), 2 Azobis compounds such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-t-butylcyclohexyl) peroxydi And peroxydicarbonates such as carbonate and diisopropylperoxydicarbonate. It can use individually or in combination of 2 or more types.
Among them, the above azobis compounds are preferably used, and azobis compounds having a 10-hour half-life temperature of 50 ° C. or more are particularly preferable. Examples of azobis compounds having a 10-hour half-life temperature of 50 ° C. or higher include 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), and 2,2′-azobis. (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropinate) and the like.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone Acetophenones such as 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Kind; Be Zophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 , 4-Dimethyl Thioxanthones such as -9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine And acyl phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; These photopolymerization initiators can be used alone or in combination of two or more.
These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

The content of the polymerization initiator (D) in the curable resin composition [i] is 100 parts by weight of the total of the binder polymer (A) component, the reactive oligomer (B) component, and the reactive monomer (C) component. When it is, it is preferable that it is 0.1-30 weight part, Especially preferably, it is 0.5-20 weight part, More preferably, it is 1-10 weight part.
If the content of the polymerization initiator (D) is too small, the coating film will be insufficiently cured and sufficient elasticity or hardness will not be obtained, and the film will become brittle and may not function, and the content is too large. When the film is stored before the reaction, the polymerization initiator (D) tends to bleed out and crystals are deposited in the coating film.

In addition, the curable resin composition [i] in the present invention may contain a filler for the purpose of improving the filling property, suppressing shrinkage during curing, improving the smoothness, and the like.
As such a filler, those having an average particle size of 0.01 μm or more and 100 μm or less can be used, and examples thereof include powders such as silicon oxide, magnesium oxide, calcium oxide, sodium carbonate, calcium carbonate, and sodium bicarbonate. . Of these, calcium carbonate powder is preferred from the viewpoint of affinity with lightweight cellular concrete (ALC), and its preferred average particle size is 0.1 to 20 μm, particularly preferably 0.1 to 10 μm. The average particle size of the filler is measured by a laser diffraction method.
The content of the filler in the curable resin composition [i] is 10 to 10 parts by weight when the total of the binder polymer (A) component, the reactive oligomer (B) component, and the reactive monomer (C) component is 100 parts by weight. The amount is preferably 1000 parts by weight, particularly preferably 30 to 500 parts by weight, and still more preferably 50 to 200 parts by weight. If the content of the filler is too small, the shrinkage and fluidity of the resin become too large, and the desired smoothness tends to be difficult to obtain. If the content is too large, the uncured film becomes brittle and the bonding property is low. In addition, the cured film becomes brittle and the resin and filler tend to fall off the surface.

  In the curable resin composition [i] in the present invention, a plasticizer, an antioxidant, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, a surfactant and the like are further known as necessary. It is possible to add these additives.

<Laminated film for concrete surface coating>
The laminated film for concrete surface coating used in the present invention comprises a layer [I] (hereinafter also referred to as a curable resin composition layer [I]) composed of a curable resin composition [i], and a support film [II]. Have a laminated structure. Moreover, as for the laminated | multilayer film for concrete surface coating, protective film [III] may be laminated | stacked on the opposite side with respect to support film [II] of curable resin composition layer [I].

The support film [II] is not particularly limited. For example, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, a polyethylene naphthalate, a polyvinyl alcohol film, an ethylene vinyl alcohol copolymer film, or a resin layer is used. It is preferable to use paper or the like laminated on the surface.
Among these, it is particularly preferable to use a PET film or paper having a resin layer laminated on the surface thereof in view of heat resistance during film formation and film curing.

  Furthermore, a pattern intended for design can be provided on the surface of the support film [II], and this pattern can be transferred to the curable resin composition layer [I] that covers the surface of the concrete after curing.

  The protective film [III] is used to prevent transfer of the curable resin composition layer [I] having adhesiveness to the support film [II] when the laminated film for covering concrete surface is rolled. Examples of such protective film [III] include polyethylene film, PET film, polypropylene film, polyvinyl alcohol film, ethylene vinyl alcohol copolymer film, polytetrafluoroethylene film, and nylon film. And release paper, among which polyethylene film and polypropylene film are preferable.

  As a method for producing a laminated film for covering a concrete surface used in the present invention, for example, a curable resin composition [i] is uniformly applied to one side of a support film [II], and usually 50 to 120 ° C. or sequentially. A method of forming the curable resin composition layer [I] by drying usually in an oven at a high temperature for 5 to 60 minutes may be mentioned. Moreover, when using protective film [III], the method of forming the said curable resin composition layer [I] and then pressure-laminating protective film [III] on the upper surface of this layer [I] is mentioned. .

In the laminated film for covering concrete surfaces used in the present invention, the thickness of the curable resin composition layer [I] is preferably 80 μm or more, particularly preferably 100 to 500 μm, more preferably 150 to 300 μm. If the thickness is too thin, there is a tendency that the number of layers to be laminated increases in order to obtain an appropriate thickness for mechanical protection on the concrete surface, so that the lamination process becomes complicated and the cost becomes too high. Alternatively, a suitable thickness cannot be obtained for protection, and it is difficult to suppress damage to the concrete surface. Moreover, when this thickness is too thick, there exists a tendency for a coating film to peel easily from the concrete surface, and there exists a tendency for cost to become high too much.
Moreover, when providing designability to the coating film which hardened curable resin composition layer [I], 150 micrometers or more are preferable and, as for the thickness of curable resin composition layer [I], especially 150- It is preferably 500 μm, more preferably 250 to 300 μm.

The laminated film for concrete surface coating thus obtained can be suitably used for surface coating of concrete, particularly surface coating of lightweight cellular concrete (ALC) board.
The ALC board has different surface properties depending on the manufacturer or lot, but it may be coated on the surface as it is, or after polishing the surface with sandpaper etc. and exposing the internal foamed part It is also possible to coat.
Below, the process of coat | covering the surface of an ALC board using the laminated | multilayer film for concrete surface coating is demonstrated.

(Lamination)
When laminating a laminated film for concrete surface coating on an ALC board as it is, it is possible to simply place the laminated film on the ALC board, but it is preferable to bond, and further, after preheating or drying the ALC board in advance. It is particularly preferable to laminate a laminated film for covering a concrete surface.
At the time of pasting, for example, it can be pasted together with a roll having a surface temperature of 70 ° C. or higher (hereinafter also referred to as a hot roll) while pressing the laminated film for covering concrete surface on the ALC board. In addition, when the laminated film for concrete surface coating has the protective film [III], the protective film [III] is peeled off or after being peeled off, and then stuck so that the curable resin composition layer [I] is in contact with the ALC board. Combined.

  The surface temperature of the hot roll at this time is preferably 80 ° C. or higher, particularly preferably 100 ° C. to 180 ° C., and more preferably 130 ° C. to 160 ° C. When the surface temperature of the heat roll is too low, the curable resin composition layer [I] of the laminated film is not sufficiently softened and melted and hardly penetrates into the ALC board surface, and the cured curable resin composition layer [ I] tends to cause peeling. If the surface temperature of the heat roll is too high, the melting of the curable resin composition layer [I] proceeds too much to reduce the viscosity, and completely penetrates the ALC board, leaving a resin component for coating on the surface. There is a tendency to disappear. Moreover, when curable resin composition [i] contains a thermal polymerization initiator, hardening of curable resin composition [i] progresses during bonding, and sufficient penetration cannot be obtained and it is curable. It tends to cause peeling of the resin composition layer [I].

The weighted linear pressure of the hot roll when pressing the laminated film for covering concrete surface is preferably 0.1 to 100 kg / cm, particularly preferably 0.3 to 50 kg / cm, more preferably 0.5 to 25 kg / cm. It is. Moreover, the moving speed of the hot roll with respect to the laminated film for concrete surface coating becomes like this. Preferably it is 0.01-20 m / min, Especially preferably, it is 0.1-15 m / min, More preferably, it is 0.2-10 m / min.
If the weighted linear pressure of the hot roll is too small or the moving speed of the hot roll is too high, the curable resin composition layer [I] of the laminated film will not sufficiently penetrate the ALC board surface, and the curability after curing will be difficult. It tends to cause peeling of the resin composition layer [I]. In addition, when the weighted linear pressure of the hot roll is too large or the moving speed of the hot roll is too low, the curable resin composition layer [I] completely penetrates into the ALC board and covers the surface. There is a tendency that no resin remains.
In addition, the roll used in the case of bonding is not restricted to said heat roll, The roll which is not heated (namely, atmospheric temperature) can also be used.

Furthermore, in order to increase the thickness of the curable resin composition layer [I] of the laminated film and obtain the desired surface shape and surface property, the curable resin composition layer [I] of this laminated film is laminated. You can also.
For example, on the first curable resin composition layer [I-1] exposed by peeling off the support film [II] of the laminated film for covering a first concrete surface bonded as described above, the second is similarly applied. The laminated film for covering a concrete surface may be laminated to laminate the first curable resin composition layer [I-1] and the second curable resin composition layer [I-2].
In addition, the first curable resin composition layer [I-1] and the second curable resin composition layer [I-2] are laminated in advance to form a thick curable resin composition layer. After that, it can be bonded to the surface of the ALC board in the same manner as described above.

[Concrete surface coating method]
In the concrete surface coating method of the present invention, as described above, the laminated film for concrete surface coating is laminated on the ALC board, so that the laminated film for concrete surface coating is laminated on the concrete, and the curable resin composition layer [I ] Is brought into contact with the concrete surface, and then placed in a bag made of a single-layer film or a multi-layer film, and the atmospheric temperature of the package sealed under reduced pressure is set to 90 ° C. or higher, or the package is irradiated with active energy rays. Then, the coating film is formed on the concrete surface by curing the curable resin composition.

(Bag made of single-layer film or multi-layer film)
A bag into which a laminate of concrete and a laminate film for covering a concrete surface is placed is a bag made of a single layer film or a multilayer film.
As the film constituting the single layer film or the multilayer film, a thermoplastic resin film can be used. Examples of the thermoplastic resin include a polyolefin film, a polyester film, a polyamide film, a polyurethane film, and a polyvinyl alcohol film. , Polycarbonate film, polystyrene film, polyacrylonitrile film, ethylene vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, ethylene-methacrylic acid copolymer film, and the like.

Examples of the resin constituting the polyolefin film include homopolymers such as polypropylene, polybutene-1, high density polyethylene, medium density polyethylene, low density polyethylene, and linear short chain branched polyethylene (LLDPE), and propylene. Ethylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,4- Copolymers with hexadiene, styrene and the like, and further graft-modified with carboxylic acids such as maleic anhydride, ethylene, propylene, butene-2, isobutylene, butadiene, pentene-1, mainly containing butene-1 With 4-methylpentene-1, hexene-1, octene-1, etc. Polymers, and further graft-modified with carboxylic acids such as maleic anhydride, propylene based on ethylene, butene-1,4-methylpentene-1,1-hexene, 1-octene, 5-ethylidene- Copolymers with 2-norbornene, 5-methylene-2-norbornene, styrene, vinyl acetate, methyl acrylate, ethyl acrylate, acrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid, glycidyl methacrylate, and the like Includes those graft-modified with a carboxylic acid such as maleic anhydride.
Among the copolymers, a copolymer with acrylic acid or methacrylic acid may be crosslinked with sodium, zinc, aluminum or the like, and a copolymer with vinyl acetate is a part of vinyl acetate component or All may be saponified. Polyethylene may be graft-modified with a carboxylic acid such as maleic anhydride.
Among the polyolefin films, a polypropylene film, a polyvinyl chloride film, a polyvinylidene chloride film, and a fluorine film are preferable.

As resin which comprises a polyester-type film, it is comprised from an acid component and a glycol component.
Examples of the acid component include terephthalic acid, oxalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. , Dimer acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, dicarboxylic acid such as cyclohexanedicarboxylic acid, 4-hydroxybenzoic acid, ε-caprolactone, oxycarboxylic acid such as lactic acid, etc. It is done.
Examples of the glycol component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, triethylene glycol, polyethylene glycol, polypropylene glycol, And glycols such as polytetramethylene glycol.

  A polyester resin is obtained by copolymerizing the above acid (component) and glycol (component). The combination of both components is not particularly limited, and those copolymerized in any combination can be used. Among them, as the polyester, polyethylene terephthalate, polyethylene naphthalate, polycyclohexylene dimethylene terephthalate is preferably used. Furthermore, polyethylene terephthalate is particularly preferably used.

  The single layer film or the multilayer film used in the present invention may be a mixture of two or more thermoplastic resins. In addition, the monolayer film or the multilayer film used in the present invention includes an ultraviolet absorber, an antioxidant, an antistatic agent, a surfactant, a pigment, a fluorescent brightening agent, and the like, and silica, calcium carbonate, titanium oxide, Organic particles containing inorganic particles, acrylic acid, styrene and the like as constituent components may be appropriately contained as necessary. Furthermore, the monolayer film or the multilayer film used in the present invention is preferably subjected to a stretching treatment, and for example, a uniaxially stretched film or a biaxially stretched film is preferably used.

The multilayer film used in the present invention has a structure in which two or more kinds of thermoplastic resin layers are laminated, and a vapor deposition layer or an adhesive layer may be interposed between the thermoplastic resin layers.
As a metal or metal oxide used for a vapor deposition layer, metals or metal oxides, such as aluminum, gold | metal | money, silver, copper, nickel, cobalt, chromium, tin, can be used, for example. Among these, aluminum, gold, silver, and tin are preferably used, and aluminum is particularly preferably used from the viewpoint of cost. The thickness of the deposited layer is usually 50 to 1000 mm, particularly 200 to 1000 mm. As a vapor deposition method of a metal or metal oxide, for example, a general vacuum vapor deposition method such as a sputtering method, an ion plating method, a resistance heating vapor deposition method, a high frequency induction heating vapor deposition method, or an electron beam heating vapor deposition method can be used. .
Examples of the adhesive in the adhesive layer include an organic titanium compound, an isocyanate compound, and a polyester compound.

  A known method can be adopted as a method for producing a single layer film or a multilayer film used in the present invention. For example, a film is formed by casting a solution of a thermoplastic resin on a metal surface such as a drum or an endless belt. The film can be formed by a casting molding method or a melt molding method by melt extrusion using an extruder.

  The thickness of the single layer film used in the present invention is usually 5 to 200 μm, and particularly preferably 10 to 100 μm. Moreover, it is preferable that the thickness of a multilayer film is 5-200 micrometers normally, especially 10-100 micrometers. If the thickness is too thin, tearing or the like tends to occur at the time of processing. Conversely, if the thickness is too thick, not only the workability is lowered but also the economy tends to be uneconomical.

  When forming a bag from a single layer film or a multilayer film, it is preferable to provide a seal layer on the inner surface of the bag. As the seal layer, a polyolefin-based resin layer is preferable from the viewpoint of seal strength, and among them, polypropylene, high-density polyethylene, low-density polyethylene, ethylene-vinyl acetate-based resin, and the like are preferably used. For the sealing layer, a film is prepared separately from the above resin, and such a film may be laminated by using an adhesive or the like on the inner surface of the bag, or on the inner surface of the bag. Direct extrusion may be used for lamination. When laminating the sealing layer as a film, laminating it as an unstretched film is advantageous in terms of obtaining sealing properties. The thickness of the sealing layer is usually 10 to 100 μm, and particularly preferably 20 to 80 μm.

  Put the laminated body of concrete and the laminated film for concrete surface coating into a bag made of the above single layer film or multilayer film, depressurize, seal the bag opening and close it to obtain a package. It is done. The degree of vacuum in the package is preferably 100 Pa or less, more preferably 10 Pa or less, and particularly preferably 5 Pa or less.

When putting a laminate of concrete and a laminate film for covering a concrete surface into a bag made of the above-mentioned single layer film or multilayer film, the laminate may be put in a bag as it is, or the surface in contact with the laminate film is You may put in a bag in the state which put the smooth flat plate or the emboss board etc. in which the unevenness | corrugation was formed in the surface which contact | connects a laminated film on the laminated film of a laminated body. In particular, it is preferable to use an embossed plate in terms of providing designability by forming irregularities on the coating film. The depth of the recess in the embossed plate is, for example, 0.001 to 1 mm, preferably 0.005 to 0.5 mm.
A flat plate, an embossed plate, or the like may be placed on the laminated film side of the packaging body in which the laminated body is put in a bag, and the following heat treatment or active energy ray irradiation may be performed.

When the curable resin composition layer [I] in the laminated film for covering a concrete surface contains a thermal polymerization initiator as the polymerization initiator (D), the ambient temperature of the package in which the laminate is sealed in the bag To 90 ° C. or higher. The atmospheric temperature is preferably 90 to 180 ° C, particularly preferably 100 to 180 ° C, and more preferably 130 to 160 ° C. Examples of a method for adjusting the ambient temperature of the package to such a temperature include, for example, a method of leaving the package in a thermostat adjusted to the ambient temperature, and the packaging in an atmosphere furnace adjusted to the ambient temperature. The method of moving the body is mentioned. The time for which the package is placed in such a temperature atmosphere is preferably 1 to 120 minutes, particularly preferably 3 to 60 minutes, and more preferably 5 to 30 minutes.
Thus, by raising the atmosphere of a package body, curable resin composition layer [I] containing a thermal-polymerization initiator raise | generates a thermosetting reaction, and turns into a desired cured film.

Next, a method for curing the curable resin composition layer [I] when the curable resin composition layer [I] contains a photopolymerization initiator will be described.
When curable resin composition layer [I] contains a photoinitiator, an active energy ray is irradiated to curable resin composition layer [I] of the laminated film for concrete surface coating through this bag. In addition, an active energy ray may be irradiated from the support film [II] side of the laminated film for concrete surface coating, or may be irradiated through a flat plate or an embossed plate on the support film [II].
As such active energy rays, for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price.
As a method of curing by ultraviolet irradiation, using a high-pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, an LED lamp, etc. The method of irradiating about 100-3000 mJ / cm < ² > is mentioned.
After the irradiation with ultraviolet rays, if necessary, heating can be performed to complete the curing.

  The laminate having the laminated film for covering a concrete surface, which is put into the bag and the curable resin composition layer [I] is cured, may be taken out from the bag or left in the bag until use. Anyway. By keeping it in the bag until use, damage during transportation and storage, dust derived from concrete, and the like can be prevented.

[End face treatment]
After being laminated on concrete such as ALC board, the laminated film for concrete surface coating that has undergone a curing reaction may cause unnecessary parts to remain due to the resin protruding from the end face of the board due to its load, etc. Unnecessary portions may be removed by cutting or cutting.
Furthermore, a resin composition that is the same as or similar to the curable resin composition [i] used in the present invention is applied to a part where the laminated film for covering the concrete surface is missing on a part of the end face or a part that cannot be laid during processing. Or a binder polymer (A) constituting the curable resin composition [i] used in the present invention or a resin similar to the binder polymer (A) may be supplemented by coating or the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “%” and “parts” mean weight basis.
The following were prepared as each component.

<Binder polymer (A)>
(A1): Polymethyl methacrylate (Mitsubishi Rayon “Dianar BR-83”)

<Reactive oligomer (B) having one or more unsaturated groups>
The following were prepared as reactive oligomers (B1).
(B1): Isophorone diisocyanate 16.1 g (0.07 mol), bifunctional polyester polyol (hydroxyl value 54 mg KOH / g) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas blowing port 2 g (0.04 mol), 0.02 g of hydroquinone monomethyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. for 3 hours to obtain 8.6 g (0.07) of 2-hydroxyethyl acrylate. The reaction was terminated when the residual isocyanate group became 0.3%, and the bifunctional urethane acrylate (B1) (weight average molecular weight 10,000, viscosity at 60 ° C. was charged. 15,000 mPa · s).

<Reactive monomer (C) having one or more unsaturated groups>
(C1): Methoxypolyethylene glycol methacrylate (“M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(C2): Condensation product of pentaerythritol and acrylic acid (corresponding to “biscoat 300” manufactured by Osaka Organic Chemical Industry Co., Ltd., trifunctional or higher monomer)

<Polymerization initiator (D)>
(D1): 2,2′-azobisisobutyronitrile (“V-60” manufactured by Wako Pure Chemical Industries, Ltd.)
(D2): 1,1′-azobis (cyclohexane-1-carbonitrile (“V-40” manufactured by Wako Pure Chemical Industries, Ltd.)

A resin solution obtained by diluting the binder polymer (A1) to 40% with ethyl acetate and an oligomer solution obtained by diluting the reactive oligomer (B1) to 70% with 2-butanone are combined with the binder polymer (A1) and the reactive oligomer (B1). ) Is mixed so that the weight ratio of the nonvolatile content is 40:60, and then the reactive monomer (C1) is further added to the total nonvolatile content of the binder polymer (A1) and the reactive oligomer (B1) of 100 parts. It mixed so that it might become 20 parts.
Next, the polymerization initiator (D1) is mixed so that the nonvolatile content of the mixture of (A1), (B1), (C1) is 2 parts with respect to 100 parts of the nonvolatile content, and the non-volatile content becomes 56%. A resin composition [i-1] solution was obtained.
This curable resin composition [i-1] solution was continuously cast on a polyester film [II] having a thickness of 25 μm by a comma coater set to a gap width of 0.5 mm, and this was further continuously added to 70%. By drying at 12 ° C. for 12 minutes and at 90 ° C. for 6 minutes, a curable resin composition layer [I-1] having a thickness of 220 μm was formed, and a laminated film for covering a concrete surface was obtained.

  The concrete surface was coated by the following five methods using the obtained laminated film for covering a concrete surface.

[Example 1]
The above concrete surface coating is applied to the surface on the outer wall side of a concrete panel ("Hebel Power Board Flat Panel" (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P) which has been dried at 80 ° C for 24 hours and then cooled to room temperature. The laminated film was obtained by laminating the curable resin composition layer [I-1] surface side of the laminated film for use. This laminate is put into a bag made of a multilayer film formed by laminating a PET film having a thickness of 25 μm and an LLDPE film having a thickness of 50 μm, and after reducing the pressure to 5 Pa, the opening of the bag is closed and the bag is closed. Sealed to obtain a package.
This sealed package is left as it is for 30 minutes in a thermostat maintained at 130 ° C. to melt the curable resin composition layer [I-1] and soak it into the surface of the panel (P). After being cured together, after cooling, the package was opened to obtain a panel laminate [α1].

[Example 2]
The above concrete surface coating is applied to the surface on the outer wall side of a concrete panel ("Hebel Power Board Flat Panel" (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P) which has been dried at 80 ° C for 24 hours and then cooled to room temperature. The laminated film was laminated so that the curable resin composition layer [I-1] surface side of the laminated film overlapped.
Thereafter, the polyester film [II] is peeled off from the laminated film, and another laminated film for covering a concrete surface produced in the same manner as described above is further formed on the curable resin composition layer [I-1]. The curable resin composition layer [I-1] was laminated so that the surface side overlapped to obtain a laminate. This laminate is put into a bag made of a multilayer film formed by laminating a PET film having a thickness of 25 μm and an LLDPE film having a thickness of 50 μm, and after reducing the pressure to 5 Pa, the opening of the bag is closed and the bag is closed. Sealed to obtain a package.
This sealed package is left as it is for 30 minutes in a thermostat maintained at 130 ° C. to melt the curable resin composition layer [I-1] and soak it into the surface of the panel (P). After being cured together, after cooling, the package was opened to obtain a panel laminate [α2].

Example 3
The above concrete surface coating is applied to the surface on the outer wall side of a concrete panel ("Hebel Power Board Flat Panel" (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P) which has been dried at 80 ° C for 24 hours and then cooled to room temperature. The laminated film was laminated so that the curable resin composition layer [I-1] surface side of the laminated film overlapped.
Thereafter, the polyester film [II] is peeled off from the laminated film, and another laminated film for covering a concrete surface produced in the same manner as described above is further formed on the curable resin composition layer [I-1]. The laminate was obtained by laminating the curable resin composition layer [I-1] side so as to overlap each other and placing an iron plate having a smooth surface on the polyester film [II] which is the outermost layer. . This laminate is put into a bag made of a multilayer film formed by laminating a PET film having a thickness of 25 μm and an LLDPE film having a thickness of 50 μm, and after reducing the pressure to 5 Pa, the opening of the bag is closed and the bag is closed. Sealed to obtain a package.
This sealed package is left as it is for 30 minutes in a thermostat maintained at 130 ° C. to melt the curable resin composition layer [I-1] and soak it into the surface of the panel (P). After being cured together, after cooling, the package was opened to obtain a panel laminate [α3].

Example 4
In Example 3, an iron plate having a smooth surface and a thickness of 3 mm is formed on a surface of a steel plate having a thickness of 3 mm that is engraved in a houndstooth pattern with squares having a depth of 100 μm and pieces of 5 mm arranged at equal intervals. A panel laminate [α4] was obtained in the same manner except that it was replaced.

Example 5
The above concrete surface coating is applied to the surface on the outer wall side of a concrete panel ("Hebel Power Board Flat Panel" (thickness 37 mm) manufactured by Asahi Kasei Construction Materials Co., Ltd.) (P) which has been dried at 80 ° C for 24 hours and then cooled to room temperature. The laminated film was laminated so that the curable resin composition layer [I-1] surface side of the laminated film overlapped.
Thereafter, the polyester film [II] is peeled off from the laminated film, and another laminated film for covering a concrete surface produced in the same manner as described above is further formed on the curable resin composition layer [I-1]. The curable resin composition layer [I-1] was laminated so that the surface side overlapped to obtain a laminate. This laminate is put into a bag made of a multilayer film formed by laminating a PET film having a thickness of 25 μm and an LLDPE film having a thickness of 50 μm, and after reducing the pressure to 5 Pa, the opening of the bag is closed and the bag is closed. Sealed to obtain a package.
A 3 mm thick iron plate with a smooth surface is placed on the bag for this sealed package, and then left in a thermostat maintained at 130 ° C. for 30 minutes to form a curable resin composition. The material layer [I-1] was melted and soaked into the surface of the panel (P) and cured, and after cooling, the package was opened to obtain a panel laminate [α5].

  For each panel laminate [α1], [α2], [α3] and [α5] of Example 1, Example 2, Example 3 and Example 5, the polyester film [II] was peeled off and each coating was performed. When a commercially available acrylic lacquer was sprayed twice on the surface of the film (cured film), a flat design surface rich in gloss was obtained. Moreover, about the panel laminated body [α4] of Example 4, the polyester film [II] was peeled off, and the surface of the coating film (cured film) was spray-coated with a commercially available acrylic lacquer twice. A surface having a staggered design in which 5 mm squares were evenly spaced was obtained.

  Put two straight cuts with a cutter knife on each coated film (cured film) surface in a cross, and paste a commercially available gum tape to cover the intersection of the cuts, and weigh 5 kg. The roll was reciprocated 10 times and bonded completely. When this gummed tape was peeled from the end portion at a constant speed of 10 m / min, peeling of the coating film was not observed at the cut portion.

  Next, the panel laminate [α1] to [α5] is fixed in the air with the surface side on which the cured film is not laminated facing up, and the panel center of the panel is struck 5 times with bare hands, From the cured film surface side, no debris was removed.

  From the above results, it is possible to form a coating film on the concrete surface by laminating a specific laminated film for concrete surface coating to concrete such as lightweight aerated concrete (ALC), and curing, so workability and production Good properties. Moreover, since the laminated | multilayer film is bonded and the concrete panel surface hardened | cured becomes smooth and is excellent in surface smoothness, it is excellent also in the design formability. Furthermore, since the laminated film can be brought into close contact with the concrete surface, it is excellent in protecting the concrete surface.

  The concrete surface covering method of the present invention can be used to increase the degree of freedom in design of the surface of concrete such as lightweight cellular concrete (ALC) used as an outer wall of a building. Moreover, the complicated painting process at the time of construction can be replaced with a process in a lightweight aerated concrete (ALC) factory, and can be used to realize simplification of on-site work. Furthermore, it can be used to reduce contamination and breakage during transportation and storage of lightweight cellular concrete (ALC).

Claims (5)

In a concrete surface coating method for forming a coating film on a concrete surface,
Binder polymer (A), reactive oligomer having at least one unsaturated group (B), Ri greens contain a reactive monomer (C) and a polymerization initiator having at least one unsaturated group (D), a binder polymer (a) is (meth) acrylic resin (a1) der Ru curable resin composition and the layer [I] composed of [i], the support film [II] and the laminated film for concrete surface coating formed by stacking Is laminated on concrete, and the curable resin composition layer [I] is brought into contact with the concrete surface, and then placed in a bag made of a single-layer film or a multi-layer film, and the atmosphere temperature of the package sealed under reduced pressure is 90 ° C. or higher. A concrete surface coating characterized in that a coating film is formed on the concrete surface by irradiating the package with active energy rays and curing the curable resin composition Law. Reactive oligomer having at least one unsaturated group (B) is a urethane (meth) acrylate compound (b1) concrete surface coating method according to claim 1, wherein it is. The method for coating a concrete surface according to claim 1 or 2, wherein the reactive monomer (C) having one or more unsaturated groups is a polyfunctional (meth) acrylate compound (c1). The concrete surface coating method according to any one of claims 1 to 3, wherein the layer [I] made of the curable resin composition [i] has a thickness of 80 µm or more. The method for covering a concrete surface according to any one of claims 1 to 4 , wherein, when sealed under reduced pressure, the degree of vacuum in the package is 100 Pa or less.