Waterproof paint, waterproof membrane, and waterproof laminate

Abstract

To provide a waterproof coating which is suitable for forming a waterproof film excellent in both high pressure scratch resistance and waterproofness.SOLUTION: There are provided a waterproof coating which contains an organic resin component, a colored pigment, an extender pigment and a solvent, and has elastic modulus of a coating film with a film thickness of 2,500 μm of 2.5-25 N / mm2 and type A durometer hardness of the coating film with a film thickness of 2,000 μm of 90 or less, and is coated onto a constituent member of a structure in the ground or water; a waterproof film formed of the waterproof coating; and a waterproof laminated film which has an epoxy resin coating film containing an epoxy resin provided below the waterproof film.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to waterproof paints, waterproof films, and waterproof laminated films. [Background technology]

[0002] When water penetrates the interior of a concrete structure, it can lead to the neutralization of the concrete or corrosion of the reinforcing steel, resulting in the deterioration of the structure over time. For this reason, waterproofing treatment is applied to the surface of concrete structures.

[0003] For example, Patent Document 1 discloses a waterproof coating method in which the surface of a concrete structure is coated with a urea resin-based primer to form a primer layer, and then coated thereon with a urethane resin-based main material containing an isocyanate group-containing prepolymer, a polyol with a molecular weight of 100 or less, and a latent curing agent.

[0004] Furthermore, in Patent Document 2, the applicant proposed a method of applying a waterproof coating material such as a urethane rubber-based coating to the roof of a structure, followed by sequentially applying a two-component curing epoxy resin-based primer, a heat-insulating paint with low thermal conductivity, a waterproof coating with a specific gravity of 1.0 or higher, and a heat-shielding paint containing a specific amount of white pigment.

[0005] According to the construction methods described in Patent Documents 1 and 2, it is possible to protect structures from sunlight, wind, and rain over a long period of time and prevent deterioration.

[0006] Thus, it has been considered common sense that preventing water from entering the interior of concrete structures requires covering them with a tough, rigid membrane. This is because, in addition to the need for a waterproof membrane that prevents water from entering, it is also required to be able to follow cracks in the substrate being treated, and therefore, it was thought that a tough, rubber-like material was necessary. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2021-17762 [Patent Document 2] Japanese Patent Publication No. 2016-142002 [Overview of the project] [Problems that the invention aims to solve]

[0008] While various attempts have been made to suppress the deterioration of outdoor structures by applying waterproofing treatments to roofs and exterior walls, attempts to coat the exterior surfaces of underground structures, in particular, have not been actively pursued, because it was thought that the effects of ultraviolet rays and oxygen are less pronounced in soil environments, and that the coating film would be damaged by the heavy loads imposed by machinery used in civil engineering work. In fact, the methods described in Patent Documents 1 and 2 are intended for outdoor structures exposed above ground, and are not intended for structures in soil environments.

[0009] The object of the present invention is to propose a waterproof coating that can be applied to structures in or underwater, capable of forming a waterproof film that is resistant to high pressure scratches and has excellent waterproofing properties. [Means for solving the problem]

[0010] The inventors of this invention diligently investigated the above-mentioned problems. As a result, they unexpectedly found that a coating that forms a soft film even when thick is effective for waterproofing structures in the ground or underwater. Furthermore, they discovered coating properties that achieve both waterproofing and high-pressure scratch resistance.

[0011] In other words, the present invention Item 1 The coating comprises an organic resin component (A), a coloring pigment (B), an extender pigment (C), and a solvent (D), and the elastic modulus of the coating film at a thickness of 2,500 μm is 2.5 to 25 N / mm². 2 A waterproof coating for application to structural components in or underwater, wherein the coating film has a Type A durometer hardness of 90 or less at a film thickness of 2,000 μm within the specified range. Section 2 A waterproof coating as described in item 1, wherein the elongation rate of the coating film at a film thickness of 2,500 μm is 200% or more. Section 3 A waterproof paint according to item 1 or 2, wherein the organic resin component mainly consists of acrylic resin. Section 4 A waterproof coating described in any one of items 1 to 3, which is a room-temperature, one-component reaction-curing type. Section 5 A water-based waterproof paint, as described in any one of items 1 to 4. Section 6 A waterproof coating according to any one of items 1 to 5, further comprising at least one selected from a crosslinking agent, organic particles, inorganic particles, lubricants, and film-forming aids. Section 7 A waterproof membrane formed by a waterproof paint described in any one of items 1 to 6. Section 8 The waterproof membrane according to item 7, provided on at least the outer surface of the aforementioned component. Section 9 A waterproof membrane as described in item 7 or 8, which is provided in advance before the construction of a structure in or underwater. Section 10 A waterproof laminated film comprising a waterproof film formed from a waterproof paint described in any one of items 1 to 6, with an epoxy resin coating film containing epoxy resin provided beneath it. Section 11 The waterproof laminated film according to claim 10, provided on at least the outer surface of the constituent member. Item 12 A waterproof laminated membrane as described in item 10 or 11, which is provided in advance before the construction of a structure in or underwater. Regarding. [Effects of the Invention]

[0012] By using the waterproof coating of the present invention to create a flexible waterproof membrane on structures in the ground or underwater, it is possible to prevent water from penetrating the interior of the structure for a long period of time, thereby extending the lifespan of the structure. Furthermore, because the formed waterproof membrane is resistant to damage even when subjected to strong loads, it can maintain its waterproof properties for a long period of time even when subjected to strong impacts by machinery during civil engineering or underwater construction.

Brief Description of the Drawings

[0013] [Figure 1] It is a figure showing an example of a test coating plate after a high-pressure resistance test.

Modes for Carrying Out the Invention

[0014] <Organic resin component (A)> In the present invention, the organic resin component (A) is not particularly limited, and either an organic solvent dilution type or a water dilution type can be used. Examples of the resin type include acrylic resin, urethane resin, fluororesin, epoxy resin, alkyd resin, silicone resin, and combinations thereof.

[0015] The organic resin component (A) is preferably contained in the non-volatile content of the waterproof coating in a range of 20 to 75% by mass, particularly 30 to 60% by mass, in terms of non-volatile content.

[0016] In this specification, the non-volatile content means the residue excluding the volatile components, and the residue may be solid or liquid at normal temperature. For example, it refers to the residual components when the sample is treated at 105°C for 3 hours to remove the volatile components.

[0017] In the present invention, it is preferable that the organic resin component (A) contains an acrylic resin from the viewpoints of high-pressure resistance and adhesion. <O000112>

[0018] Examples of the acrylic resin include resins obtained by copolymerizing a polymerizable unsaturated monomer component containing a (meth)acryloyl compound as an essential component and other polymerizable unsaturated monomers.

[0019] Examples of (meth)acryloyl compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and "isostearyl acrylate" (manufactured by Osaka Organic Chemical Co., Ltd., ISTA). Linear or branched alkyl (meth)acrylates such as highly branched long-chain alkyl acrylates; alicyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate; fluoroalkyl (meth)acrylates such as hexafluoroisopropyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; (2-acryloyloxyethyl) acid phosphate, (2-methacryloyloxyethyl) Phosphate-containing (meth)acrylates such as (2-ethyl) acid phosphate, (2-acryloyloxypropyl) acid phosphate, and (2-methacryloyloxypropyl) acid phosphate; N,N-dialkylaminoalkyl (meth)acrylates such as N,N-diethylaminoethyl (meth)acrylate; (meth)acrylamide; (meth)acrylic acid; carbonyl-containing (meth)acryloyl monomers such as acetoacetoxyethyl (meth)acrylate and diacetone (meth)acrylamide; epoxy-containing (meth)acryloyl monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, and 3,4-epoxycyclohexylpropyl (meth)acrylate;(Meth)acryloyl monomers containing isocyanato group, such as isocyanatoethyl (meth)acrylate; (Meth)acryloyl monomers containing alkoxysilyl group, such as γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltriethoxysilane; Polyvinyl compounds such as allyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol di(meth)acrylate, 1,1,1-trishydroxymethylethane di(meth)acrylate, 1,1,1-trishydroxymethylethane tri(meth)acrylate, and 1,1,1-trishydroxymethylpropane tri(meth)acrylate; (Meth)acrylates containing oxidatively curable groups such as dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxypropyl (meth)acrylate, and dicyclopentenyl (meth)acrylate; 1,2,2,6,6-pentamethylpiperidyl (meth)acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)acrylate, etc.; 2-(methacryloyloxy)ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, methacryloylaminopropyltrimethylammonium chloride, methacryloylaminopropyltrimethylammonium bromide, tetrabutylammonium (meth)acrylate, tetramethylammonium (meth)acrylate, trimethylbenzylammonium (meth)acrylate, and 2-(methacryloyloxy)ethyltrimethylammonium dimethyl phosphate; (meth)acrylates having polyoxyalkylene chains with alkoxy groups at the molecular end; These are some examples, and each can be used individually or in combination of two or more.

[0020] Other polymerizable unsaturated monomers include, for example, (meth)acrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl aromatic compounds such as styrene and α-methylstyrene; carboxyl group-containing polymerizable unsaturated monomers such as maleic acid, crotonic acid, and β-carboxyethyl acrylate; carbonyl group-containing polymerizable unsaturated monomers such as (meth)acrolein, formyl styrene, vinyl alkyl ketones with 4 to 7 carbon atoms (e.g., vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), and acetoacetoxyaryl esters; and epoxy group-containing polymers such as allyl glycidyl ether. Examples include polymerizable unsaturated monomers; polymerizable unsaturated monomers containing isocyanate groups such as m-isopropenyl-α,α-dimethylbenzyl isocyanate; polymerizable unsaturated monomers containing alkoxysilyl groups such as vinyltrimethoxysilane and vinyltriethoxysilane; polymerizable unsaturated monomers containing oxidative curable groups, such as reaction products of epoxy group-containing polymerizable unsaturated monomers or hydroxyl group-containing polymerizable unsaturated monomers with unsaturated fatty acids; and fluorovinyl ethers such as fluoroalkyl trifluorovinyl ethers and perfluoroalkyl trifluorovinyl ethers. These can be used individually or in combination of two or more types.

[0021] The weight-average molecular weight of the acrylic resin can be adjusted as appropriate, but it can be in the range of 10,000 to 3,000,000, and especially 50,000 to 1,000,000.

[0022] In this specification, the weight-average molecular weight is the value obtained by converting the weight-average molecular weight measured by a gel permeation chromatograph (HLC8120GPC, manufactured by Tosoh Corporation) to the weight-average molecular weight of polystyrene. Four columns were used: "TSKgel G-4000H×L", "TSKgel G-3000H×L", "TSKgel G-2500H×L", and "TSKgel G-2000H×L" (all manufactured by Tosoh Corporation, trade names). The measurements were performed under the following conditions: mobile phase; tetrahydrofuran, measurement temperature; 40°C, flow rate; 1 cc / min, detector; radioisotope (RI).

[0023] The waterproof coating of the present invention is preferably a room-temperature, one-component reaction-curing type from the viewpoint of ease of application and waterproofing performance. For this reason, it is preferable that the acrylic resin contains a carbonyl group-containing polymerizable unsaturated monomer as a copolymer component.

[0024] Examples of polymerizable unsaturated monomers containing a carbonyl group include acetoacetoxyethyl (meth)acrylate, diacetone (meth)acrylamide, (meth)acrolein, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, acetoacetoxyaryl ester, and combinations thereof.

[0025] The copolymerization ratio of the carbonyl group-containing polymerizable unsaturated monomer is preferably in the range of 1 to 20% by mass, more preferably 3 to 15% by mass, of the total polymerizable unsaturated monomer used in the production of acrylic resin.

[0026] Furthermore, from the viewpoint of resistance to high-pressure scratches, the acrylic resin preferably contains an acrylate containing a linear or branched alkyl group with 4 or more carbon atoms as a copolymer component.

[0027] Examples of acrylates containing linear or branched alkyl groups having 4 or more carbon atoms include n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and combinations thereof.

[0028] The copolymerization ratio of the acrylate containing the linear or branched alkyl group having 4 or more carbon atoms is preferably 50% by mass or more, more preferably 65-85% by mass, in the total polymerizable unsaturated monomer used in the production of acrylic resin.

[0029] Furthermore, it is preferable that the above organic resin component includes, as part of its components, an acrylic resin in which the copolymerization ratio of an acrylate containing a linear or branched alkyl group having 4 or more carbon atoms is less than 50% by mass.

[0030] Examples of polymerizable unsaturated monomers and linear or branched alkyl groups having 4 or more carbon atoms used in the acrylic resin include the compounds exemplified above.

[0031] In the present invention, from the viewpoint of high-pressure scratch resistance, it is preferable to use in combination an acrylic resin (a1) in which the copolymerization ratio of acrylate containing linear or branched alkyl groups having 4 or more carbon atoms is 50% by mass or more in the total polymerizable unsaturated monomer used in the production of the acrylic resin, and an acrylic resin (a2) in which the copolymerization ratio of acrylate containing linear or branched alkyl groups having 4 or more carbon atoms is less than 50% by mass in the total polymerizable unsaturated monomer used in the production of the acrylic resin. The combined ratio is suitable in the range of 5 / 95 to 95 / 5.

[0032] In the present invention, if the acrylic resin is aqueous, it may be either an emulsion type or a water-soluble type, but an emulsion type is preferred.

[0033] Emulsion-type acrylic resins can be produced, for example, by emulsion polymerization of the polymerizable unsaturated monomer component in one or multiple steps, in the presence of water and a dispersion stabilizer.

[0034] <Coloring pigment (B)> The coloring pigment (B) contained in the waterproof coating of the present invention may be an inorganic or organic pigment, used alone or in combination. Examples of inorganic pigments include titanium dioxide, yellow iron oxide, red iron oxide, carbon black, and combinations thereof. Examples of organic pigments include azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, phthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and combinations thereof.

[0035] <Extender pigment (C)> Examples of the extender pigment (C) include calcium carbonate, clay, silica, barium sulfate, talc, white carbon, diatomaceous earth, magnesium aluminum carbonate flakes, mica flakes, and combinations thereof.

[0036] In the present invention, the above-mentioned coloring pigment (B) and extender pigment (C) are preferably included in such a way that the total pigment volume concentration is 10 to 60 vol%, more preferably 15 to 55 vol%, from the viewpoint of high-pressure scratch resistance and waterproofing. In this specification, the pigment volume concentration is the volume ratio of the pigment to the total solid content of the total resin and total pigment in the paint. In this specification, the specific gravity of the pigment used as the basis for calculating the volume of the pigment is from "Dictionary of Pigments" (editor-in-chief: Seijiro Ito), and the specific gravity of the resin solids is assumed to be approximately 1.

[0037] <Solvent (D)> The waterproof coating of the present invention contains solvent (D). By including solvent (D), it is possible to provide durability through a waterproof film even if the surface of the component to be coated has a complex shape or an intricate structure.

[0038] The solvent contained in the aforementioned waterproofing paint can be any volatile substance that does not remain on the film after painting, and may be an organic compound or water. However, it is preferable that the main component is water and the waterproofing paint is water-based, given the favorable working environment.

[0039] The term "aqueous" is used in contrast to "organic solvent system," and generally refers to a medium that is water or primarily composed of water (aqueous medium), while an "organic solvent system" means that it does not substantially contain water as a solvent, or that all or most of the solvent is an organic solvent.

[0040] <Waterproof paint> The waterproof coating of the present invention comprises an organic resin component, a coloring pigment, an extender pigment, and a solvent, and the elastic modulus of the coating film at a thickness of 2,500 μm is 2.5 to 25 N / mm². 2 Within the specified range, the paint has a Type A durometer hardness of 90 or less at a film thickness of 2,000 μm.

[0041] In this invention, by using a paint in which the elastic modulus and type A durometer hardness are within the above range, both high-pressure scratch resistance and waterproofing can be achieved.

[0042] In this specification, the modulus of elasticity can be determined as follows: A sample is coated onto a polypropylene plate to a dry film thickness of 2,500 μm, dried at 23°C for 7 days, the coating is peeled off the polypropylene plate, and the sample is cut into strips 20 mm long and 5 mm wide. Using a uniaxial tensile testing machine "EZ-TEST EZ-LX HS" (manufactured by Shimadzu Corporation, product name), the sample is pulled longitudinally until it breaks under the conditions of a measurement temperature of 23°C, a tensile speed of 50 mm / min, and a chuck distance of 10 mm, and the longitudinal axis is measured as stress (N / mm²). 2 A stress-strain curve is obtained with strain (%) on the horizontal axis. Next, the modulus of elasticity is calculated from the tangent line at the rising edge of the obtained stress-strain curve.

[0043] The Type A durometer hardness is preferably 50 or higher, and more preferably 55 or higher, from the viewpoint of achieving both high-pressure scratch resistance and waterproofing. Type A durometer hardness is determined by coating a steel plate with a dry film thickness of 2,000 μm, drying it at 23°C for 7 days, and measuring the hardness using a durometer ("Asker Rubber Hardness Tester Type A," trade name, manufactured by ASKER) in accordance with JIS K 6253-3 2012, at a measurement temperature of 23°C. The measurement must be performed within 1 second of placing the test specimen in the testing machine.

[0044] Furthermore, the waterproof coating of the present invention is more preferably a coating that forms a coating film with an elongation of 200% or more, preferably in the range of 500 to 1,300%, from the viewpoint of high-pressure scratch resistance and adhesion.

[0045] The elongation rate is the ratio of the length increase at the time of fracture to the original length before the test. The measurement can be performed under the same conditions as described above for the elastic modulus.

[0046] To adjust the elastic modulus, type A durometer hardness, and elongation, for example, methods such as preparing the composition of the organic resin component (A), or adjusting the ratio of the organic resin component (A) to the coloring pigment (B) and extender pigment (C) are used.

[0047] <Other ingredients> The waterproof coating of the present invention preferably further contains at least one selected from a crosslinking agent, organic particles, inorganic particles, lubricant, and film-forming aid, from the viewpoint of waterproofing and resistance to high-pressure scratches.

[0048] Among these, known crosslinking agents include, specifically, amino resins, polyisocyanate compounds, polyhydrazide compounds, polysemicarbazide compounds, carbodiimide group-containing compounds, oxazoline group-containing compounds, epoxy compounds, polycarboxylic acids, and the like.

[0049] The use of polyhydrazide compounds is particularly preferred.

[0050] Specific examples of polyhydrazide compounds include, for example, dihydrazides of saturated aliphatic carboxylic acids having 2 to 18 carbon atoms, such as oxalate dihydrazide, malonic acid dihydrazide, succinate dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacate dihydrazide; dihydrazides of monoolefinic unsaturated dicarboxylic acids, such as maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide; dihydrazides of phthalic acid, terephthalic acid, or isophthalic acid; and pyrome Examples include dihydrazides, trihydrazides, or tetrahydrazides of littic acid; trihydrazides of nitrilotriacetate, trihydrazides of citrate, and 1,2,4-benzenetrihydrazides; tetrahydrazides of ethylenediaminetetraacetate and tetrahydrazides of 1,4,5,8-naphthoate; polyhydrazides obtained by reacting low polymers having lower alkyl ester groups of carboxylic acids with hydrazine or hydrazine hydrate (hydrazine hydrade), and combinations thereof.

[0051] From the viewpoint of resistance to high-pressure scratches, the crosslinking agent content is preferably in the range of 0.01 to 5.0 parts by mass, more preferably 0.02 to 0.8 parts by mass, based on 100 parts by mass of the non-volatile content of the waterproofing paint.

[0052] Examples of the organic particles include particles formed from polyacrylate resin, polymethacrylate resin, polyolefin resin, polystyrene resin, polyamide resin, polyamino acid resin, polyester resin, polyurethane resin, polyvinyl chloride resin, cellulose resin, melamine resin, urea resin, epoxy resin, fluororesin, and mixtures thereof. The organic particles may be commercially available products, such as the Gantz Pearl series and Stafiloid series from Aica Kogyo Co., Ltd., the ChemiPearl series from Mitsui Chemicals Co., Ltd., the Art Pearl series from Negami Kogyo Co., Ltd., the Eposter series from Nippon Shokubai Co., Ltd., the ToughTic series from Toyobo Co., Ltd., and the Techpolymer series from Sekisui Kasei Co., Ltd.

[0053] Examples of inorganic particles include silica particles. Powdered silica, colloidal silica, etc., can be used as silica particles. Commercially available silica particles may also be used. Examples of commercially available silica particles include the Aerosil series from Nippon Aerosil Co., Ltd., the Carplex series from Evonik Industries, Ltd., Sealdex from Asahi Glass Co., Ltd., the Silicia series from Fuji Silicia Co., Ltd., the Snowtex series from Nissan Chemical Corporation, and the Adelite series from ADEKA Corporation.

[0054] The above organic or inorganic particles can be used alone or in combination. Preferably, the content is 0.5 to 10% by mass, particularly 1.0 to 8.0% by mass, in terms of nonvolatile content within the nonvolatile content of the waterproofing paint.

[0055] The waterproof coating of the present invention preferably contains a lubricant from the viewpoint of resistance to high-pressure scratches. Examples of lubricants include waxes, silicone compounds, and perfluoroalkyl compounds. Examples of waxes include paraffin wax, polyolefin wax, ester wax which is a condensate of a fatty acid and a monohydric or polyhydric alcohol, and carnauba wax. It is preferable to add the wax as wax particles contained in an aqueous emulsion in which the wax is dispersed in water. The aforementioned wax may be a commercially available product, such as the AQUACER series, CERACOL series, and CERAFLOUR series from BYK Corporation, and the ChemiPearl series from Mitsui Chemicals Corporation.

[0056] Examples of silicone compounds include polysiloxane-based surfactants and polyether-modified polysiloxanes.

[0057] Examples of perfluoroalkyl compounds include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds.

[0058] The above lubricants can be used alone or in combination. Preferably, the content is within the range of 0.1 to 10% by mass, particularly 0.5 to 5.0% by mass, in terms of non-volatile content within the non-volatile content of the waterproofing paint.

[0059] The waterproof coating of the present invention preferably contains a film-forming aid from the viewpoint of alkali resistance. Examples of film-forming aids include glycol ethers such as ethylene glycol monoisopropyl ether, ethylene glycol dibutyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, diethylene glycol dibutyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether; ester compounds such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol mono-2-ethylhexanoate, and 2,2,4-trimethyl-1,3-pentanediol di-2-ethylhexanoate. These can be used individually or in combination of two or more types.

[0060] The above film-forming aids can be used alone or in combination. In terms of content, from the viewpoint of alkali resistance, it is preferable that the non-volatile content of the waterproofing paint be 5.0% by mass or less, and particularly within the range of 0.1 to 2.5% by mass.

[0061] In addition to the components described above, the waterproof coating of the present invention may contain paint additives such as plasticizers, thickeners, defoamers, dispersants, flame retardants, and neutralizing agents as needed.

[0062] <Waterproof membrane> The waterproof coating of the present invention is applied to components for constructing structures in the ground or underwater, and dried to form a waterproof film on the surface of the components. There are no particular restrictions on the material of the components, but examples include components made of metals such as iron, zinc, aluminum, and magnesium; components made of alloys of these metals; concrete, stone, plastic; and combinations thereof.

[0063] There are no particular restrictions on specific examples of structures; any structure constructed in the ground or underwater can be included.

[0064] Furthermore, since the waterproof membrane of the present invention has excellent resistance to pressure damage, the effects of the present invention can be maximized by providing it on at least the outer surface (soil side or water side) of the structural components, and by providing it in advance before the construction of the structure.

[0065] The dry film thickness of the waterproof film of the present invention described above is preferably in the range of 100 to 5,000 μm, more preferably 500 to 3,000 μm, from the viewpoint of adhesion, high-pressure scratch resistance, and waterproofing. In this specification, the dry film thickness shall be determined by theoretical calculation from the amount of coating on a non-volatile content basis.

[0066] Painting methods include, for example, rollers, air sprayers, airless sprayers, texture guns, all-purpose guns, and brushes, and multiple coats can be applied to achieve the desired dry film thickness.

[0067] The formed waterproof membrane can be dried at room temperature, but heating may be used if necessary.

[0068] <Waterproof laminated membrane> In the present invention, a waterproof laminated film may be formed by providing an epoxy resin coating film containing epoxy resin beneath the waterproof film of the present invention.

[0069] The underlying epoxy resin coating consists mainly of epoxy resin, which is cured by mixing it with a hardening agent. Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resin. Examples of hardening agents include polyamines such as ethylenediamine and diethylenetriamine, amine adducts obtained by adding epoxy resin to the aforementioned polyamines, and various other polyamines.

[0070] The dry film thickness of the epoxy resin coating is preferably in the range of 10 to 200 μm, more preferably 30 to 150 μm.

[0071] Painting methods for forming an epoxy resin coating include, for example, rollers, air sprayers, airless sprayers, resin guns, all-purpose guns, and brushes, and multiple coats can be applied to achieve the target dry film thickness.

[0072] The formed epoxy resin coating can be dried at room temperature, but heating may be performed if necessary. [Examples]

[0073] The present invention will be further described below with reference to examples. Here, unless otherwise specified, 'parts' and '%' mean 'parts by mass' and '% by mass', respectively.

[0074] <Manufacturing of waterproof paints> Examples 1, 7~ 21. Reference Examples 1 and 2, and Comparative Example 1~ 3 Each waterproofing paint (X-1) to (X-21) was manufactured using the formulations listed in Tables 1 and 2 below.

[0075] <Formation of a waterproof membrane> Example 1~ 21. Reference Examples 1 and 2, and Comparative Example 1~ 3 A waterproof film was formed using the aforementioned waterproof paints (X-1) to (X-21), and the following evaluation tests were conducted. The property values ​​listed in the table were measured and calculated in accordance with the methods described in the specification.

[0076] [Table 1]

[0077] [Table 2]

[0078] (Note 1) 50% acrylic resin emulsion (a1): Emulsified polymer of styrene / n-butyl acrylate / 2-ethylhexyl acrylate / methacrylic acid / diacetone acrylamide = 10 / 1 / 80 / 3 / 6, weight-average molecular weight 300,000 (Note 2) 50% acrylic resin emulsion (a2): Emulsified polymer of styrene / n-butyl acrylate / 2-ethylhexyl acrylate / methyl methacrylate / hydroxyethyl acrylate / acrylic acid / diacetone acrylamide / 1,6-hexamethylene diacrylate = 15 / 24 / 15 / 41 / 2 / 0.3 / 2.3 / 0.4 (Note 3) Coloring pigment: Titanium dioxide, specific gravity 4.1 (Note 4) Extender pigment: Calcium carbonate, specific gravity 2.7 (Note 5) 33% colloidal silica: "Snowtex O-33", product name, manufactured by Nissan Chemical Corporation (Note 6) 80% resin particles: "Gantzpearl GM-1702H", product name, manufactured by Aica Kogyo Co., Ltd. (Note 7) 50% wax emulsion: "AQUACER497", product name, manufactured by BYK. (Note 8) Polyetherpolysiloxane: "TEGOGlide410", trade name, manufactured by Evonic. (Note 9) Film-forming aid: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Note 10) Urethane-based waterproof coating material: Main agent: Tolylene diisocyanate and polypropylene glycol-based terminal isocyanate urethane prepolymer / xylene = 24 / 1 Hardener: Polypropylene glycol / plasticizer / calcium carbonate / titanium oxide / carbon black / xylene = 10 / 7 / 46 / 0.3 / 0.1 / 6 two-component waterproof material Mass ratio of main agent to hardener is 1:3 (Note 11) Epoxy / amine-based anticorrosive paint: Main agent: Bisphenol A-type epoxy resin with an epoxy equivalent of 190 / bisphenol F-type epoxy resin with an epoxy equivalent of 190 / titanium oxide / talc / xylene = 60 / 40 / 5 / 5 / 2 Hardener: Aromatic polyamide amine with an amine value of 360 / titanium oxide / xylene = 20 / 25 / 2 Mass ratio of main agent to hardener is 2:1.

[0079] <Evaluation test> (*) Waterproofness: Each waterproof paint shown in the table was applied to a polypropylene plate to achieve the film thickness shown in the table, and dried at 23°C for 7 days to obtain a free film. In this invention, a test was conducted in accordance with BS EN14150 as a test for reproducing groundwater pressure and confirming the waterproofness of the coating film. Specifically, a free film was sandwiched in a cell provided in a waterproof tester (manufactured by Kansai Paint Co., Ltd.), the inside of the tester was filled with water, and then pressure was applied to both sides of the free film, with one side under high pressure (0.15 MPa) and the opposite side under low pressure (0.05 MPa), to create a pressure difference, and the amount of water passing through the film was measured and evaluated according to the following criteria. ◎: Less than 0.05 [L / m 2 / day], 〇: 0.05 [L / m 2 / day] or more and 0.1 [L / m 2 / day] or less, △: More than 0.1 [L / m 2 / day] and 0.5 [L / m 2 / day] or less, ×: More than 0.5 [L / m 2 / day]. If the rating is ◎ or ○, it means that the product meets the BTS CLASS3 standard and that water permeability is well suppressed even under high pressure. If the rating is △ or ×, it means that the waterproofing is insufficient under groundwater pressure conditions and it is judged to be unsuitable for practical use.

[0080] (*) High pressure scratch resistance: A black steel plate (70mm wide x 150mm long x 2.3mm thick) was used as a support. A paint mixture of the main component and hardener ("ESCO NB," manufactured by Kansai Paint Co., Ltd., a two-component ketimine-curing modified epoxy resin rust-preventive paint) was applied to the plate to a dry film thickness of 60μm. After drying at 23°C for 8 hours, each waterproof paint listed in the table was applied to the plate to the film thickness listed in the table. The plates were dried at 23°C for 7 days to create test coated plates. At room temperature of 23°C, a high-pressure scratch resistance tester (manufactured by Kansai Paint Co., Ltd.) was used to observe the surface condition of each test coated plate. A backing plate (SUS304H spring steel plate) was held at a 45-degree angle, and a load of 100kg was applied. The test coated plate was moved 100mm at a speed of 10mm / second, and the surface condition was observed and evaluated according to the following criteria. Figure 1 shows an example of a test coated plate after the high-pressure scratch resistance test. In this example, damage such as dents, gouges, and scale marks is observed. ◎: No damage whatsoever is observed, such as dents, gouges, or scale marks. ○: Some damage such as dents, gouges, and scale marks is visible, but no metal base material is visible at all. △: Damage such as dents, gouges, and scale marks is observed, and the bare metal is also visible. ×: The painted surface peels off completely. A rating of ◎ indicates particularly excellent resistance to high-pressure scratches, while a rating of ○ means the scratches do not reach the metal substrate, making it suitable for practical use. On the other hand, ratings of △ and × indicate that the scratches reach the metal substrate, making it unsuitable for practical use.

[0081] (*) Alkali resistance: Each waterproof coating listed in the table was applied to a polypropylene board to the thickness specified in the table, and dried at 23°C for 7 days to obtain a free film. This free film was immersed in saturated limewater at 50°C for 56 days and subjected to the waterproofing test described above. The evaluation criteria were the same as those for the waterproofing test. If the rating is ◎ or ○, it means that the product meets the BTS CLASS3 standard, and water permeability is well suppressed even under high pressure and in an alkaline atmosphere like concrete. If the rating is △ or ×, it means that the waterproofing is insufficient under groundwater pressure and an alkaline environment, and it is judged to be unsuitable for practical use.

[0082] (*)Drying: A test coating panel was prepared using the same method as in the high-pressure scratch resistance test described above, and the amount of residue remaining after pressing and peeling off tissue paper from the surface of the coating film was evaluated according to the following criteria. ◎: The painted surface is completely non-sticky, and tissue paper does not stick to it. ○: The paint film surface is slightly sticky, but the tissue paper peeled off without leaving any residue. △: The paint film surface is sticky, and a small amount of tissue paper remains. ×: The coating adheres to the tissue paper. A rating of ◎ indicates particularly excellent drying properties, and a rating of ○ means no tissue paper residue is left behind, making it practical for everyday use. On the other hand, ratings of △ and × indicate stickiness and adhesion to tissue paper, making it difficult to transport waterproofed components, and thus unsuitable for practical use.

[0083] (*)Adhesion: Test coated panels were prepared using the same method as the high-pressure scratch resistance test described above, and their adhesion was examined using the pull-off test method in accordance with JIS K5600-5-7 (2014). The measurement area of ​​each test panel was lightly sanded clean with sandpaper, and then attached to a 20 mm diameter dolly (test cylinder) using adhesive. The coating around the dolly was cut with a cutter, the dolly was peeled off with a tester, and the strength (MPa) at that time was observed and evaluated according to the following criteria. ◎: The strength was 0.9 MPa or higher. ○: The strength was 0.6 MPa or higher and less than 0.9 MPa. △: The strength was 0.3 MPa or higher and less than 0.6 MPa. ×: The strength was less than 0.3 MPa. If the evaluation is ◎ or ○, it means that the adhesion strength standard of the Road Bridge Deck Waterproofing Manual is met and the waterproof coating has sufficient adhesion. If the evaluation is △ or ×, it means that the above standard is not met and the coating is deemed unacceptable.

[0084] Although embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the embodiments described above, and various modifications based on the technical concept of the present invention are possible.

Claims

1. A waterproof coating for application to structural components in or underwater, comprising an organic resin component (A), a coloring pigment (B), an extender pigment (C), and a solvent (D), wherein the elastic modulus of the coating film at a thickness of 2,500 μm is in the range of 2.5 to 25 N / mm2, and the Type A durometer hardness of the coating film at a thickness of 2,000 μm is 90 or less, The elongation rate of the coating film at a thickness of 2,500 μm is 200% or more. A waterproof paint in which the organic resin component (A) mainly consists of acrylic resin.

2. The waterproof coating according to claim 1, which is a room-temperature, one-component reaction-curing type.

3. The waterproof paint according to claim 1, which is a water-based paint.

4. The waterproof coating according to claim 1, further comprising at least one selected from a crosslinking agent, organic particles, inorganic particles, a lubricant, and a film-forming aid.

5. A waterproof film formed by a waterproof paint according to any one of claims 1 to 4.

6. The waterproof membrane according to claim 5, provided on at least the outer surface of the aforementioned component.

7. The waterproof membrane according to claim 5, which is provided in advance before the construction of a structure in the ground or underwater.

8. A waterproof laminated film comprising a waterproof film formed from a waterproof paint according to any one of claims 1 to 4, with an epoxy resin coating film containing epoxy resin provided beneath it.

9. The waterproof laminated film according to claim 8, provided on at least the outer surface of the aforementioned component.

10. The waterproof laminated membrane according to claim 8, which is provided in advance before the construction of a structure in the ground or underwater.

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