Coating composition

Abstract

The present invention provides a coating composition that yields a film with excellent water repellency and superior UV resistance. [Solution] A coating composition comprising (A) polyester, (B) a plasticizer, and (C) water, wherein component (A) comprises a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound.

Description

[Technical Field]

[0001] The present invention relates to a coating composition, a method for manufacturing a coating composition, a coating composition, a hydraulic composition, a method for manufacturing a hydraulic composition, and a method for forming a coating layer. [Background technology]

[0002] Painting is widely used for purposes such as rust prevention, surface protection, and aesthetic enhancement in ships, buildings, bridges, and other structures. Various types and functionalities of paints are known to be used for such applications. For example, in the field of concrete, hydrophobic coatings are sometimes applied to the concrete surface to prevent neutralization of concrete due to acid rain and to prevent a decrease in durability due to alkali-silica reaction caused by the penetration of water droplets. Hydrophobic coatings include polyurea resin coatings and siloxane-based coatings.

[0003] Patent Document 1 discloses a film-forming curing agent for preventing initial drying during the curing of concrete, which is applied to the exposed surface of the poured concrete after a predetermined hardening period and after the formwork has been removed, and is a material mainly composed of a water-dispersible polyester. Furthermore, Patent Document 2 discloses a concrete coating agent for preventing carbonation and salt damage to concrete, which is a material mainly composed of a water-dispersible polyester and is applied to the exposed surface of the concrete. Furthermore, Patent Document 3 discloses a paint composition containing a silane coupling agent having alkoxy and amino groups with 1 to 5 carbon atoms, a resin obtained by neutralizing a polyester with an acid value of 3 to 100 KOH mg / g with a base, water, and hollow particles made of inorganic material, with a specific gravity of 0.85 to 0.95. Furthermore, Patent Document 4 discloses a polyester emulsion for asphalt modification that contains polyester particles with a volume median particle size (D50) of 20 nm to 500 nm and water. In addition, Patent Document 5 discloses an emulsion resin composition containing (A) an aliphatic polyester resin and (B) an ester plasticizer.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] When the coating film becomes brittle due to ultraviolet degradation or the like, the functions of the coating are lost. For example, a film that has undergone a chemical reaction or oxidation by ultraviolet rays tends to become hydrophilic, and the effect of preventing rainwater from entering the concrete interior becomes weak. When maintenance work such as recoating the coating agent is required, the working cost increases significantly, so the durability of the hydrophobic coating is required. The present invention provides a coating composition capable of obtaining a film having excellent water repellency and excellent ultraviolet resistance, a method for producing the coating composition, a coating composition, a hydraulic composition, a method for producing the hydraulic composition, and a method for forming a coating layer.

Means for Solving the Problems

[0006] In one embodiment, the present invention provides a coating composition comprising (A) polyester, (B) a plasticizer, and (C) water, wherein component (A) comprises a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound.

[0007] Furthermore, in another embodiment, the present invention provides a method for producing a coating composition, comprising mixing (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

[0008] In another embodiment, the present invention provides a coating composition formed from a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

[0009] Furthermore, in another embodiment, the present invention provides a hydraulic composition comprising a hardened body of a hydraulic composition and a coating layer provided on the surface of the hydraulic composition, wherein the coating layer is formed from a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

[0010] Furthermore, in another embodiment, the present invention provides a method for producing a hydraulic composition, which involves applying a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water to the surface of a mixture of hydraulic powder and water.

[0011] Furthermore, in another embodiment, the present invention provides a method for forming a coating layer, which includes applying a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water to one or more surfaces selected from hydraulic composition surfaces and metal surfaces. [Effects of the Invention]

[0012] The present invention provides a coating composition that has excellent water repellency and yields a film with excellent ultraviolet resistance, a method for manufacturing the coating composition, the coating composition, a hydraulic composition, a method for manufacturing the hydraulic composition, and a method for forming a coating layer. [Modes for carrying out the invention]

[0013] The mechanism by which the coating composition of the present invention forms a coating with excellent water repellency and excellent UV resistance is not clear, but it is presumed to be as follows. It is believed that the polyester component (A), containing a polycondensate of polyethylene terephthalate, alcohol, and a carboxylic acid compound, can form a coating with excellent water repellency and UV resistance. This is presumed to be because the polyethylene terephthalate chains are not completely decomposed and exist within the polyester molecule as units of a certain length, resulting in a block polymer-like structure consisting of hydrophilic parts derived from polyethylene terephthalate and other hydrophobic parts. The hydrophilic parts then accumulate at the boundary between the coating surface and the surface of the object (e.g., a concrete surface), and by strongly interacting with the hydrophilic interface of the object, the adhesion of the coating film is improved. On the other hand, it is presumed that the hydrophobic parts accumulate at the boundary between the coating surface and the air, causing the coating to exhibit hydrophobicity. Polyethylene terephthalate is inherently a highly polar polyester and is more hydrophilic. Surprisingly, however, in this invention, it is presumed to contribute to improving the hydrophobicity of the coating film. Furthermore, it is presumed that the molecular structure, such as the block polymer described above, contributes to improving the UV resistance of the coating. These effects enable the coating composition of the present invention to provide a hydrophobic coating with high water repellency and excellent UV resistance, thereby extending the lifespan of the coating and reducing maintenance work. Furthermore, the coating composition, method for manufacturing the coating composition, coating composition, hydraulic composition, method for manufacturing the hydraulic composition, and method for forming a coating layer of the present invention are not limited to the above-described mechanism of action.

[0014] [Coating composition] In exemplary embodiments, the coating composition of the present invention comprises (A) polyester [hereinafter referred to as component (A)], (B) plasticizer [hereinafter referred to as component (B)], and (C) water [hereinafter referred to as component (C)], wherein component (A) comprises a polycondensate of polyethylene terephthalate, alcohol, and a carboxylic acid compound. The coating composition of the present invention may be a hydrophobic coating composition, and more particularly, a hydrophobic coating composition for hydraulic compositions. In the present invention, a hydrophobic coating may be a coating that forms a water-repellent film on a target surface.

[0015] <(A) component> Component (A) is polyester. Component (A) may be a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound. Component (A) may be used in one or more forms.

[0016] The polyester of component (A) comprises polyethylene terephthalate, an alcohol, and a polycondensate of a carboxylic acid compound. Component (A) is preferably a compound in which the alcohol contains an alkylene oxide adduct of bisphenol A.

[0017] <Alcohol> (A) The alcohols from which the constituent units of component (A) are derived include, for example, one or more selected from aliphatic diols, aromatic diols, and polyhydric alcohols of trihydric or higher hydricity, and from the viewpoint of further enhancing the hydrophobicity of the coating film, preferably includes an alkylene oxide adduct of bisphenol A, and more preferably includes an alkylene oxide adduct of bisphenol A represented by the following formula (I).

[0018] [ka] [In the formula, OR 1 and R 1 O is an alkylene oxide, and R 1 x is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers representing the average number of added moles of alkylene oxide, and the sum of x and y is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, and even more preferably 4 or less. Alternatively, the sum of x and y is preferably 1 to 16, more preferably 1.5 to 8, and even more preferably 1.5 to 4.

[0019] Examples of alkylene oxide adducts of bisphenol A represented by formula (I) include propylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These alkylene oxide adducts of bisphenol A can be used individually or in combination of two or more.

[0020] From the viewpoint of further enhancing the hydrophobicity of the coating film, the amount of bisphenol A alkylene oxide adduct used is preferably 20 mol% or more, more preferably 30 mol% or more, and 95 mol% or less, of 100 mol% of the alcohol constituting the polyester of component (A). Alternatively, from the viewpoint of further enhancing the hydrophobicity of the coating film, the amount of bisphenol A alkylene oxide adduct used is preferably 20 mol% to 95 mol%, more preferably 30 mol% to 95 mol%, of 100 mol% of the alcohol constituting the polyester of component (A). In other words, in component (A), the content of constituent units derived from the alkylene oxide adduct of bisphenol A is preferably 20 mol% or more, more preferably 30 mol% or more, and 95 mol% or less, out of 100 mol% of the alcohol-derived constituent units constituting the polyester of component (A), from the viewpoint of further enhancing the hydrophobicity of the coating film. Alternatively, in component (A), the content of constituent units derived from the alkylene oxide adduct of bisphenol A is preferably 20 mol% to 95 mol%, more preferably 30 mol% to 95 mol%, out of 100 mol% of the alcohol-derived constituent units constituting the polyester of component (A), from the viewpoint of further enhancing the hydrophobicity of the coating film. The alcohol constituting the polyester of component (A) also includes ethylene glycol, which constitutes polyethylene terephthalate. In other words, the alcohol-derived constituent units constituting component (A) also include constituent units of component (A) that are derived from ethylene glycol of polyethylene terephthalate. The same applies hereafter to descriptions regarding the amount or content of alcohol-derived constituent units unless otherwise specified.

[0021] (A) The alcohols from which the constituent units of component (A) are derived may include alcohols other than the alkylene oxide adduct of bisphenol A. Examples of alcohols other than the alkylene oxide adduct of bisphenol A include aliphatic diols, aromatic diols (excluding those corresponding to the alkylene oxide adduct of bisphenol A), and polyhydric alcohols of trihydric or higher hydricity. These alcohols can be used individually or in combination of two or more.

[0022] Aliphatic diols include, for example, one or more selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. Aromatic diols include, for example, one or more selected from 1,3-benzenediol, 1,4-benzenediol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and 4,4'-diphenyldimethanol. A polyhydric alcohol with a valency of three or higher is, for example, a trihydric alcohol. Glycerin is an example of a polyhydric alcohol with a valency of three or higher.

[0023] <Carboxylic acid compounds> (A) The carboxylic acid compounds from which the constituent units of component (A) are derived include, for example, one or more selected from aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and polycarboxylic acid compounds with a valency of 3 to 6. These carboxylic acid compounds can be used individually or in combination of two or more.

[0024] From the viewpoint of further enhancing the hydrophobicity of the coating film, the number of carbon atoms in the main chain of the aliphatic dicarboxylic acid compound is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Alternatively, from the viewpoint of further enhancing the hydrophobicity of the coating film, the number of carbon atoms in the main chain of the aliphatic dicarboxylic acid compound is preferably 3 to 10, more preferably 4 to 8. Examples of aliphatic dicarboxylic acid compounds include fumaric acid, maleic acid, oxalic acid, malonic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, or their anhydrides, or their alkyl esters (for example, alkyl groups having 1 to 3 carbon atoms). Examples of substituted succinic acid include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among the above aliphatic dicarboxylic acid compounds, one or more selected from the group consisting of dodecenyl succinic acid, its anhydride, and adipic acid are preferred, and dodecenyl succinic acid or its anhydride are more preferred.

[0025] Examples of aromatic dicarboxylic acid compounds include phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or their anhydrides, or their alkyl esters (for example, alkyl groups with 1 to 3 carbon atoms). Among these aromatic dicarboxylic acid compounds, from the viewpoint of further enhancing UV resistance, one or more selected from the group consisting of isophthalic acid and terephthalic acid are preferred, with terephthalic acid being more preferred.

[0026] The polycarboxylic acid with a valency of 3 to 6 is preferably a tricarboxylic acid. Examples of polycarboxylic acids with a valency of 3 to 6 include trimellitic acid, 2,5,7-naphthalentricarboxylic acid, pyromellitic acid, or their acid anhydrides. When a polycarboxylic acid is included, from the viewpoint of adjusting physical properties, the alcohol may appropriately contain a monovalent alcohol, and the carboxylic acid compound may appropriately contain a monovalent carboxylic acid compound.

[0027] When the carboxylic acid compound includes an aliphatic dicarboxylic acid compound, the content of the aliphatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and preferably 30 mol% or less, and more preferably 25 mol% or less, out of 100 mol% of the carboxylic acid compound-derived structural units. Alternatively, if the carboxylic acid compound includes an aliphatic dicarboxylic acid compound, the content of the aliphatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) is preferably 1 mol% to 30 mol%, more preferably 3 mol% to 25 mol%, and even more preferably 5 mol% to 25 mol%, out of 100 mol% of the carboxylic acid compound-derived structural units, from the viewpoint of further enhancing UV resistance. Furthermore, the content of constituent units derived from carboxylic acid compounds in component (A) includes the content of constituent units of component (A) that are derived from terephthalic acid of polyethylene terephthalate. The same applies to descriptions of the content of constituent units derived from carboxylic acid compounds hereafter, unless otherwise specified. The content of a constituent unit in component (A) may be the amount of the compound from which that constituent unit is derived. The same applies to the other constituent units in component (A) below.

[0028] When the carboxylic acid compound includes an aromatic dicarboxylic acid, the content of the aromatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less, from the viewpoint of further improving ultraviolet resistance. Alternatively, if the carboxylic acid compound includes an aromatic dicarboxylic acid, the content of the aromatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) is preferably 60 mol% to 100 mol%, more preferably 65 mol% to 99 mol%, even more preferably 70 mol% to 95 mol%, and even more preferably 75 mol% to 90 mol%, out of 100 mol% of the carboxylic acid compound-derived structural units.

[0029] (Molar ratio of constituent units derived from carboxylic acid compounds to constituent units derived from alcohols) (A) In component (A), the molar ratio of constituent units derived from the carboxylic acid compound to constituent units derived from the alcohol [(carboxylic acid compound) / (alcohol)] is preferably 0.7 or higher, more preferably 0.8 or higher, even more preferably 0.9 or higher, and preferably 1.5 or lower, more preferably 1.3 or lower, and even more preferably 1.1 or lower, from the viewpoint of further enhancing the hydrophobicity of the coating film. Alternatively, the molar ratio [(carboxylic acid compound) / (alcohol)] is preferably 0.7 to 1.5, more preferably 0.8 to 1.3, and even more preferably 0.9 to 1.1, from the viewpoint of further enhancing the hydrophobicity of the coating film.

[0030] (Constituent units derived from polyethylene terephthalate) (A) The polyester component contains structural units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate. In addition to the structural units consisting of ethylene glycol and terephthalic acid, polyethylene terephthalate may also contain small amounts of other components such as butanediol and isophthalic acid.

[0031] In recent years, the environmental impact of waste plastics has become a concern, and the recycling of waste plastics is being considered. In this invention, since polyethylene terephthalate is commonly used in products such as bottles and films, polyethylene terephthalate that has been manufactured as such products and subsequently discarded and then recovered (hereinafter also referred to as "recycled PET") is preferably used from the standpoint of environmental issues and cost. That is, from the viewpoint of reducing environmental burden and improving economic efficiency, recycled polyethylene terephthalate is preferred as the source of the constituent units of component (A). Furthermore, the type of collected material is not particularly limited, as long as it possesses a certain level of purity. It may contain small amounts of plastics such as polyethylene or polypropylene as impurities.

[0032] In component (A), the content of constituent units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, from the viewpoint of further enhancing the hydrophobicity and ultraviolet resistance of the coating film. Alternatively, in the component (A), from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film, the content of the structural unit composed of ethylene glycol and terephthalic acid derived from polyethylene terephthalate is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, still more preferably 30 parts by mass or more and 40 parts by mass or less, per 100 parts by mass of the structural units of the component (A). The content (parts by mass) of the structural unit composed of ethylene glycol and terephthalic acid derived from polyethylene terephthalate may be the total content (parts by mass) of the structural unit derived from ethylene glycol constituting polyethylene terephthalate and the structural unit derived from terephthalic acid constituting polyethylene terephthalate.

[0033] (U of the structural unit derived from the alkylene oxide adduct of bisphenol A in the polyester of the component (A) B ) and the structural unit (U E ) composed of ethylene glycol and terephthalic acid derived from polyethylene terephthalate, the molar ratio [(U B ) / (U E )] is preferably 20 / 80 or more, more preferably 30 / 70 or more, still more preferably 35 / 65 or more, and preferably 95 / 5 or less, more preferably 90 / 10 or less, still more preferably 80 / 20 or less, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film. Alternatively, the molar ratio [(U B ) / (U E )] is preferably 20 / 80 or more and 95 / 5 or less, more preferably 30 / 70 or more and 90 / 10 or less, still more preferably 35 / 65 or more and 80 / 20 or less, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film.

[0034] The polyester used in the present invention may be a modified polyester to the extent that its properties are not substantially impaired. Specifically, modified polyesters include polyesters that have been grafted or blocked with phenol, urethane, epoxy, etc., by methods described in Japanese Patent Publication No. 11-133668, Japanese Patent Publication No. 10-239903, Japanese Patent Publication No. 8-20636, etc. A preferred modified polyester is a urethane-modified polyester obtained by urethane stretching of polyester with a polyisocyanate compound.

[0035] (Physical properties of polyester) (A) The softening point of the polyester component is preferably 85°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 140°C or lower, more preferably 130°C or lower, even more preferably 125°C or lower, even more preferably 120°C or lower, and even more preferably 115°C or lower, from the viewpoint of further enhancing the hydrophobicity of the coating film. Alternatively, from the viewpoint of further enhancing the hydrophobicity of the coating film, this softening point is preferably 85°C to 140°C, more preferably 90°C to 130°C, even more preferably 95°C to 125°C, even more preferably 95°C to 120°C, and even more preferably 95°C to 115°C.

[0036] (A) The acid value of the polyester component is preferably 2 mg KOH / g or more, more preferably 3 mg KOH / g or more, and even more preferably 5 mg KOH / g or more, from the viewpoint of further enhancing the stability of the coating film, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 25 mg KOH / g or less, from the viewpoint of further enhancing the hydrophobicity of the coating film. Alternatively, from the viewpoint of further enhancing the stability and hydrophobicity of the coating film, the acid value is preferably 2 mg KOH / g or more and 40 mg KOH / g or less, more preferably 3 mg KOH / g or more and 30 mg KOH / g or less, and even more preferably 5 mg KOH / g or more and 25 mg KOH / g or less.

[0037] (A) The hydroxyl value of the polyester component is preferably 1 mg KOH / g or more, more preferably 2 mg KOH / g or more, even more preferably 5 mg KOH / g or more, and even more preferably 10 mg KOH / g or more, and preferably 70 mg KOH / g or less, more preferably 50 mg KOH / g or less, even more preferably 40 mg KOH / g or less, and even more preferably 30 mg KOH / g or less, from the viewpoint of further enhancing the stability of the coating film. Alternatively, from the viewpoint of further enhancing the stability of the coating film, the hydroxyl value is preferably 1 mg KOH / g or more and 70 mg KOH / g or less, more preferably 2 mg KOH / g or more and 50 mg KOH / g or less, even more preferably 5 mg KOH / g or more and 40 mg KOH / g or less, and even more preferably 10 mg KOH / g or more and 30 mg KOH / g or less.

[0038] The glass transition temperature of the polyester component (A) is preferably 30°C or higher, more preferably 40°C or higher, even more preferably 50°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower, from the viewpoint of further enhancing the hydrophobicity of the coating film. Alternatively, from the viewpoint of further enhancing the hydrophobicity of the coating film, this glass transition temperature is preferably 30°C to 80°C, more preferably 40°C to 70°C, and even more preferably 50°C to 65°C.

[0039] (A) The polyester component has a weight-average molecular weight (Mw) of preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, from the viewpoint of further enhancing UV resistance, and preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less, from the viewpoint of further enhancing the stability of the coating film. Alternatively, the weight-average molecular weight (Mw) of the polyester in component (A) is preferably 1,000 to 100,000, more preferably 5,000 to 70,000, and even more preferably 10,000 to 50,000, from the viewpoint of further improving UV resistance and the stability of the coating film.

[0040] (A) The weight-average molecular weight (Mw) of component can be determined by measuring the molecular weight distribution using gel permeation chromatography (GPC). (i) Preparation of sample solution Dissolve component (A) in tetrahydrofuran at 25°C to a concentration of 0.5 g / 100 mL. Then, filter this solution using a fluoropolymer filter with a pore size of 0.2 μm (Toyo Roshi Co., Ltd., "DISMIC-25JP") to remove undissolved components and obtain the sample solution. (ii) Measurement of weight-average molecular weight Using the measuring apparatus and analytical column described below, tetrahydrofuran is flowed as the eluent at a flow rate of 1 mL / min, and the column is stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution is then injected and the measurement is performed. The weight-average molecular weight of the sample is calculated based on a pre-prepared calibration curve. The calibration curve includes several types of monodisperse polystyrene "A-500" (5.0 × 10⁻¹⁰). 2 ), "A-1000" (1.01 x 10 3 ), "A-2500" (2.63 x 10 3 ), "A-5000" (5.97 x 10 3 ), "F-1" (1.02×10 3 ), "F-2" (1.81×10 4 ), "F-4" (3.97×10 4 ), "F-10" (9.64×10 4 ), "F-20" (1.90×10 5 ), "F-40" (4.27×10 5 ), "F-80" (7.06×10 5 ), "F-128" (1.09×10 6 The above samples were prepared using Tosoh Corporation's standard samples. Measuring device: "HLC-8220CPC" (manufactured by Tosoh Corporation) Analysis columns: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[0041] The softening point, acid value, hydroxyl value, and glass transition point of the polyester of component (A) can be measured by the method described in the examples. The softening point, acid value, hydroxyl value, and glass transition point can be adjusted by the raw material monomer composition, molecular weight, catalyst amount, or reaction conditions.

[0042] From the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film, component (A) preferably has a heat generation of 10 J / g or less, more preferably 5 J / g or less, even more preferably 3 J / g or less, and preferably 0 J / g or more, as measured by differential scanning calorimetry (DSC) at 240°C to 260°C, and may be 0 J / g. Alternatively, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film, component (A) may have a heat generation amount of 0 J / g or more and 10 J / g or less, more preferably 0 J / g or more and 5 J / g or less, and even more preferably 0 J / g or more and 3 J / g or less, as measured by differential scanning calorimetry (DSC) at 240°C to 260°C, and may be 0 J / g. Differential scanning calorimetry is performed using the following method. If the heat generation amount in differential scanning calorimetry is "-", it indicates that the absolute value is the heat absorption amount. The polyethylene terephthalate raw material for component (A) exhibits a large exothermic peak in the range of 240°C to 260°C. Therefore, the fact that the exothermic amount of component (A) in differential scanning calorimetry (DSC) measurements in the 240°C to 260°C range is within this range suggests that the polyethylene terephthalate raw material reacted well with the alcohol and carboxylic acid compounds and was introduced into the polyester backbone.

[0043] (Differential scanning calorimetry) (A) Differential scanning calorimetry (DSC) measurement of component (A) is performed using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.). 0.01 to 0.02 g of the sample is weighed into an aluminum pan and heated to 300°C at a heating rate of 10°C / min. A baseline is drawn over the exothermic behavior portion, including the maximum peak temperature, and its area is defined as the amount of heat released. Similarly, a baseline is drawn over the endothermic behavior portion, including the maximum peak temperature, and its area is defined as the amount of heat absorbed.

[0044] (Method of manufacturing polyester) The method for producing the polyester of component (A) is not particularly limited, but for example, it can be produced by polycondensation of polyethylene terephthalate, the alcohol, and the carboxylic acid compound, or by polycondensation of polyethylene terephthalate, the alcohol containing an alkylene oxide adduct of bisphenol A, and the carboxylic acid compound. The temperature of the polycondensation reaction is not particularly limited, but from the viewpoint of reactivity and monomer decomposition temperature, it is preferably 210°C to 260°C.

[0045] Polyethylene terephthalate is a crystalline resin, and due to strong intermolecular interactions, it is difficult to form a uniform aqueous dispersion. It tends to aggregate and precipitate due to intermolecular interactions, making it difficult to form a uniform film on the target surface. In the polyester manufacturing method of the present invention, it is preferable to react polyethylene terephthalate and the monomer component simultaneously, from the viewpoint of forming a uniform film on the target surface. By reacting polyethylene terephthalate and the monomer component simultaneously, the polyethylene terephthalate chain is decomposed and the interaction is weakened, allowing a uniform film to be formed on the target surface.

[0046] The amount of polyethylene terephthalate present in the raw materials is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, out of 100% by mass of the total amount of polyethylene terephthalate, the alcohol, and the carboxylic acid compound. Alternatively, the amount of polyethylene terephthalate present in the raw materials is preferably 1% to 50% by mass, more preferably 10% to 45% by mass, and even more preferably 30% to 40% by mass, out of 100% by mass of the total amount of polyethylene terephthalate, alcohol, and carboxylic acid compound.

[0047] By adding polyethylene terephthalate during the polycondensation reaction between the alcohol and the carboxylic acid compound, a transesterification reaction occurs, and a polyester can be obtained in which the constituent units of polyethylene terephthalate are incorporated into the constituent units derived from the alcohol and the constituent units derived from the carboxylic acid compound. Polyethylene terephthalate may be present from the start of the polycondensation reaction or added to the reaction system during the polycondensation reaction. From the viewpoint of further improving the stability of the coating film composition and the uniformity of the hydrophobic coating film, the timing of adding polyethylene terephthalate is preferably when the reaction rate between the alcohol and the carboxylic acid compound is 10% or less, and more preferably when it is 5% or less. The reaction rate is defined as the value of [amount of reaction water produced (moles) / theoretical amount of water produced (moles)] × 100.

[0048] For the polycondensation reaction, a tin(II) compound that does not have a Sn-C bond, such as di(2-ethylhexanoate)tin(II), can be used as an esterification catalyst from the viewpoint of reactivity and cost. The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and preferably 3.0 parts by mass or less, and more preferably 1.5 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol, the carboxylic acid compound and polyethylene terephthalate. In the polycondensation reaction, from the viewpoint of reactivity and cost, pyrogallol derivatives such as gallic acid can be used as esterification co-catalysts in addition to the catalyst. When using an esterification co-catalyst, the amount of the esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and preferably 0.50 parts by mass or less, more preferably 0.20 parts by mass or less, and even more preferably 0.10 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol, the carboxylic acid compound and polyethylene terephthalate.

[0049] Component (A) is preferably a polyester containing alcohol-derived structural units and carboxylic acid-derived structural units. Component (A) is a polymer containing a polyester that, from the viewpoint of further enhancing ultraviolet resistance, includes alcohol-derived structural units and carboxylic acid-derived structural units, wherein the content of aromatic dicarboxylic acid-derived structural units in the total amount of carboxylic acid-derived structural units contained in the polyester is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less. Alternatively, from the same viewpoint, the content of aromatic dicarboxylic acid-derived constituent units in the total amount of constituent units derived from carboxylic acid compounds contained in the polyester is preferably 60 mol% to 100 mol%, more preferably 65 mol% to 99 mol%, even more preferably 70 mol% to 95 mol%, and even more preferably 75 mol% to 90 mol%.

[0050] <(B) component> (B) Component is a plasticizer. (B) Component may be used in one or more forms.

[0051] Component (B) is not particularly limited, as long as it has the effect of imparting flexibility to component (A) by interacting with component (A) used in the present invention. (B) Component is preferably one or more selected from aliphatic esters, aromatic esters, and phosphate esters, more preferably one or more selected from aliphatic esters and aromatic esters, and even more preferably one or more selected from aromatic esters, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film.

[0052] Aliphatic esters include, for example, one or more selected from monohydric alcohol esters of fatty acids, monohydric alcohol esters of polybasic acids, and fatty acid esters of polyhydric alcohols, and more specifically, one or more selected from 2-ethylhexyl oleate and tributyl acetylcitrate (ATBC). Aromatic esters include, for example, one or more selected from diallyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, bis(2-ethylhexyl) phthalate, and tris-2-ethylhexyl trimellitate. Examples of phosphate esters include one or more selected from tributoxyethyl phosphate and tris(2-ethylhexyl) phosphate.

[0053] (B) Component has a specific gravity of preferably 0.85 or higher, more preferably 0.90 or higher, even more preferably 0.95 or higher, and even more preferably 1.00 or higher, from the viewpoint of further enhancing the hydrophobicity of the coating film, and preferably 1.20 or lower, more preferably 1.18 or lower, and even more preferably 1.15 or lower, from the viewpoint of further enhancing the stability of the coating composition. Alternatively, from the viewpoint of further enhancing the hydrophobicity and stability of the coating film, this specific gravity is preferably 0.85 to 1.20, more preferably 0.90 to 1.18, even more preferably 0.95 to 1.15, and even more preferably 1.00 to 1.15. The aforementioned specific gravity may be the specific gravity at 25°C.

[0054] The molecular weight of component (B) is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more, from the viewpoint of volatility, and preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less, from the viewpoint of affinity with component (A). Alternatively, from the viewpoint of volatility and affinity with component (A), the molecular weight is preferably 100 to 600, more preferably 150 to 550, and even more preferably 200 to 500.

[0055] <(C) component> The coating composition of the present invention contains (C) water. For example, deionized water, tap water, or purified water can be used. The water can be used as the remainder of the composition in an amount such that the overall composition of the composition is 100% by mass.

[0056] <Composition, etc.> The coating composition of the present invention contains component (A) in an amount of preferably 8% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of further enhancing the ultraviolet resistance of the coating film. Alternatively, the coating composition of the present invention contains component (A) in an amount of preferably 8% to 70% by mass, more preferably 10% to 60% by mass, even more preferably 20% to 50% by mass, and even more preferably 30% to 50% by mass, from the viewpoint of further enhancing the ultraviolet resistance of the coating film.

[0057] The coating composition of the present invention contains component (B) in an amount of preferably 2% by mass or more, more preferably 3% by mass or more, from the viewpoint of further enhancing the hydrophobicity of the coating film, and preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of further enhancing the stability of the coating composition. Alternatively, the coating composition of the present invention contains component (B) in an amount of preferably 2% to 15% by mass, more preferably 3% to 13% by mass, and even more preferably 3% to 10% by mass, from the viewpoint of further enhancing the hydrophobicity and stability of the coating film.

[0058] In the coating composition of the present invention, the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is preferably 0.05 or more, more preferably 0.08 or more, even more preferably 0.10 or more, and from the viewpoint of further improving the hydrophobicity and ultraviolet resistance of the coating film, preferably 0.3 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. Alternatively, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film, this mass ratio [(B) / (A)] is preferably 0.05 or more and 0.3 or less, more preferably 0.08 or more and 0.25 or less, and even more preferably 0.10 or more and 0.20 or less.

[0059] The coating composition of the present invention contains component (C) in an amount of preferably 28% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and even more preferably 60% by mass or more, from the viewpoint of further enhancing the stability of the coating composition, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of further enhancing the hydrophobicity and ultraviolet resistance of the coating film. Alternatively, the coating composition of the present invention contains component (C) in an amount of preferably 28% to 90% by mass, more preferably 40% to 80% by mass, even more preferably 50% to 70% by mass, and even more preferably 60% to 70% by mass, from the viewpoint of further enhancing the stability, hydrophobicity, and ultraviolet resistance of the coating composition.

[0060] <(D) component> The coating composition of the present invention may optionally contain a neutralizing agent (D) [hereinafter referred to as component (D)] from the viewpoint of further enhancing the stability of the coating composition. Component (D) may be one or more types. Component (D) may be, for example, a neutralizing agent that neutralizes the carboxyl group of component (A). Examples of carboxyl groups of component (A) include terminal carboxyl groups of polyester and carboxyl groups generated by the partial decomposition of polyester.

[0061] Component (D) may include, for example, basic substances. Basic substances may include one or more selected from alkali metal hydroxides, ammonia, alkylamines, and alkylalkanolamine nitrogen-containing basic substances. Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide; examples of alkylamines include trimethylamine; and examples of alkylalkanolamine nitrogen-containing basic substances include diethanolamine.

[0062] If the coating composition of the present invention contains component (D), the coating composition of the present invention contains component (D) in an amount of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, from the viewpoint of further enhancing the stability of the coating composition. Alternatively, if the coating composition of the present invention contains component (D), the coating composition of the present invention contains component (D) in an amount of preferably 0.1% to 2% by mass, more preferably 0.2% to 1.5% by mass, from the viewpoint of further enhancing the stability of the coating composition.

[0063] <(E) component> The coating composition of the present invention may optionally contain (E) an organic solvent [hereinafter referred to as component (E)] from the viewpoint of further enhancing the stability of the coating composition. Component (E) may be one or more selected from ether-based organic solvents and ketone-based organic solvents. Specifically, ether-based solvents may include tetrahydrofuran, and ketone-based organic solvents may include acetone and methyl ethyl ketone. From the viewpoint of further enhancing the stability of the coating composition, methyl ethyl ketone is preferred for component (E).

[0064] If the coating composition of the present invention contains component (E), the coating composition of the present invention contains component (E) in an amount of preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, from the viewpoint of further enhancing the hydrophobicity of the coating film, and preferably 0.1% by mass or less, more preferably 0.01% by mass or less, from the viewpoint of further enhancing the stability of the coating film. Alternatively, if the coating composition of the present invention contains component (E), the coating composition of the present invention contains component (E) in an amount of preferably 0.0001% by mass or more and 0.1% by mass or less, and more preferably 0.001% by mass or more and 0.01% by mass or less, from the same viewpoint.

[0065] The coating composition of the present invention may optionally contain a thermoplastic resin other than that which corresponds to component (A). The thermoplastic resin may be one or more selected from, for example, poly(meth)acrylic acid, poly(meth)acrylic acid ester, styrene-acrylic copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber, and preferably one or more selected from styrene-acrylic copolymer and styrene-butadiene rubber.

[0066] The coating composition of the present invention has a glass transition temperature of the solid obtained by drying the coating composition, which is preferably -20°C or higher, more preferably -10°C or higher, even more preferably -5°C or higher, and from the same viewpoint, preferably 30°C or lower, more preferably 20°C or lower, and even more preferably 15°C or lower, in order to further enhance the hydrophobicity and ultraviolet resistance of the coating film. Alternatively, from the viewpoint of further enhancing the hydrophobicity and UV resistance of the coating film, this glass transition temperature is preferably -20°C to 30°C, more preferably -10°C to 20°C, and even more preferably -5°C to 15°C. The glass transition temperature of the solid content obtained by drying the coating composition can be measured by the method described in the examples.

[0067] The coating composition of the present invention may be a coating composition comprising component (A), component (B), and component (C). Furthermore, the coating composition of the present invention may be a coating composition further comprising the above-mentioned optional components. In the coating composition of the present invention, the preferred amounts of component (A), component (B), and component (C) can be applied by replacing the preferred content in the above-described coating composition of the present invention with the amounts of the components. Furthermore, in the coating composition of the present invention, the mass ratio of the amount of each component can be applied by replacing the mass ratio of the preferred content in the coating composition of the present invention with the mass ratio of the amount of each component.

[0068] The coating composition of the present invention may be a composition for coating one or more surfaces selected from hydraulic composition surfaces and metal surfaces. The hydraulic composition may be concrete. The hydraulic composition may be a hydraulic composition containing a hydraulic powder and water, which will be described in detail later. Examples of metals include iron, aluminum, and stainless steel.

[0069] The coating composition of the present invention can be used, for example, by applying, scattering, or spraying it onto a target surface to form a coating on the target surface. Specifically, this includes applying the hydraulic composition to the surface using a brush or mop, or spraying it with a sprayer. The coating composition of the present invention can be applied, for example, to the exposed surface of concrete after a predetermined hardening period, and then the hydraulic composition can be hardened to obtain a coating with excellent water repellency and excellent UV resistance. Furthermore, the coating composition of the present invention can be used, for example, as a coating composition for surfaces during maintenance or repair of cement mortar structures, concrete structures, and flooring materials.

[0070] <Method for producing coating compositions> In an exemplary embodiment, the present invention provides a method for producing a coating composition by mixing (A) a polyester [component (A)] comprising a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer [component (B)], and (C) water [component (C)]. This manufacturing method produces the coating composition of the present invention containing component (A), component (B), and component (C). In the method for producing the coating composition of the present invention, (D) a neutralizing agent [which is component (D)] may be optionally mixed in. Furthermore, in the method for producing the coating composition of the present invention, any of the optional components listed in the coating composition of the present invention may be optionally mixed in. Specific examples of components (A), (B), (C), (D), and other optional components used in the method for producing the coating composition of the present invention, as well as preferred embodiments, are the same as those described in the description of the coating composition of the present invention. The matters described in the present invention concerning the coating composition can be applied to the method for producing the coating composition of the present invention. In the method for producing the coating composition of the present invention, the content of each component and their mass ratio described in the coating composition of the present invention can be applied by replacing the content of each component with the amount of mixture.

[0071] <Coating composition> In exemplary embodiments, the present invention provides a coating composition formed from a coating composition comprising (A) a polyester [component (A)] comprising a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer [component (B)], and (C) water [component (C)]. The coating composition of the present invention may be a coating composition formed by spraying or applying a coating composition containing component (A), component (B), and component (C) to one or more surfaces selected from hydraulic composition surfaces and metal surfaces. The hydraulic composition may be concrete. In the coating composition of the present invention, the coating composition may further optionally contain (D) a neutralizing agent [which is component (D)]. Furthermore, in the coating composition of the present invention, the coating composition may optionally contain any of the components listed in the coating composition of the present invention.

[0072] Specific examples of component (A), component (B), component (C), component (D), and other optional components, as well as preferred embodiments, in the coating composition of the present invention are the same as those described in the coating composition of the present invention. The matters described in the coating composition of the present invention can be applied to the coating composition used in the coating composition of the present invention. In the coating composition of the present invention, the content of each component in the coating composition and their mass ratios can be those described in the coating composition of the present invention. Furthermore, the preferred embodiments of the coating composition and the specific methods for spraying or applying the coating composition can also be those described in the description of the coating composition of the present invention.

[0073] The coating composition of the present invention may be a coating composition formed by spraying or applying the coating composition of the present invention to one or more surfaces selected from hydraulic composition surfaces and metal surfaces.

[0074] From the viewpoint of further enhancing water repellency and UV resistance, the coating composition is preferably 100 g / m². 2 Above, a comfortable 150g / m 2 In addition to the above, and from the standpoint of working time and cost, 250g / m² is preferable. 2 More preferably 200g / m² 2 It is preferable to apply the following amounts to the target surface, and more preferably to spray or coat the target surface with the aforementioned amounts. Alternatively, the coating amount is preferably 100 g / m², from the viewpoint of further enhancing water repellency and UV resistance. 2 More than 250g / m 2 More preferably, 150 g / m² 2 More than 200g / m 2 The following applies:

[0075] <Hydraulic composition> In exemplary embodiments, the present invention provides a hydraulic composition comprising a cured body of a hydraulic composition and a coating layer provided on the surface of the hydraulic composition, wherein the coating layer is formed from a coating composition comprising (A) a polyester [component (A)] containing a polycondensate of polyethylene terephthalate, alcohol, and a carboxylic acid compound, (B) a plasticizer [component (B)], and (C) water [component (C)]. The hydraulic composition may be a cured body obtained by curing a hydraulic composition containing hydraulic powder and water. Furthermore, the surface of the hydraulic composition may be the surface of a cured body of the hydraulic composition. The hydraulic composition of the present invention comprises a hardened body of the hydraulic composition and a coating layer provided on the surface of the hydraulic composition, wherein the coating layer may be formed by spraying or applying a coating composition containing component (A), component (B), and component (C). The hydraulic composition of the present invention may be a hydraulic composition comprising a hardened body of the hydraulic composition and a coating layer provided on the surface of the hydraulic composition, the coating layer containing component (A) and component (B). In the hydraulic composition of the present invention, the coating composition may optionally contain (D) a neutralizing agent [which is component (D)]. Furthermore, the hydraulic composition of the present invention may be a hydraulic composition in which the coating composition of the present invention is scattered or applied to the hydraulic composition. The components (A), (B), (C), and (D) used in the hydraulic composition of the present invention, as well as specific examples of the coating composition and preferred embodiments, are the same as those described for the coating composition of the present invention. The matters described in the coating composition and manufacturing method of the present invention can be applied to the hydraulic composition of the present invention.

[0076] <Hydraulic powder> The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and examples include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R5214). Among these, from the viewpoint of strength development, one or more cements selected from rapid-hardening Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement are preferred, and one or more cements selected from rapid-hardening Portland cement and ordinary Portland cement are more preferred. Furthermore, the hydraulic powder may contain blast furnace slag, fly ash, silica fume, calcined clay, anhydrous gypsum, etc., and may also contain non-hydraulic limestone fine powder, etc. As the hydraulic powder, blast furnace cement, fly ash cement, silica fume cement, or calcined clay mixed cement, which are mixtures of cement with blast furnace slag, fly ash, silica fume, calcined clay, etc., may be used. It may also contain clay such as bentonite. The hydraulic compositions obtained by adding sand, sand and gravel as aggregate to these powders are generally called mortar, concrete, etc., respectively.

[0077] <Aggregates> The hydraulic composition of the present invention may optionally contain aggregate. The aggregate may be one or more types of aggregate selected from fine aggregate and coarse aggregate. Examples of fine aggregate include those specified in JIS A0203-2014, item number 2311. Examples of fine aggregate include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Furthermore, coarse aggregates include those specified in number 2312 of JIS A 0203-2014. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone of these, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Fine aggregate and coarse aggregate may be mixed together or used as a single type.

[0078] A coating layer containing component (A) and component (B) can be formed by applying a coating composition containing component (A), component (B), and component (C) to the surface of a hydraulic composition. Methods for applying the composition to the surface of the hydraulic composition include, for example, coating or spraying. Specifically, the composition can be applied to the surface of the hydraulic composition using a roller, a hand pump sprayer, or a sprayer. A coating composition comprising component (A), component (B), and component (C) may be the coating composition of the present invention. Accordingly, the content of component (A), the content of component (B), the content of component (C), and the mass ratio of these contents [(B) / (A)] in the coating composition are the same as those described in the embodiment of the coating composition of the present invention.

[0079] A coating composition containing component (A), component (B), and component (C), and furthermore, the coating composition of the present invention, is preferably 100 g / m² from the viewpoint of further enhancing water repellency and UV resistance. 2 Above, a comfortable 150g / m 2 In addition to the above, and from the standpoint of working time and cost, 250g / m² is preferable. 2 More preferably 200g / m² 2 Use the following application amounts on the surface of the hydraulic composition. Alternatively, from the viewpoint of further enhancing water repellency and UV resistance, as well as from the viewpoint of work time and cost, the amount of coating applied is preferably 100 g / m². 2 More than 250g / m 2 More preferably, 150 g / m² 2 More than 200g / m 2 The following applies:

[0080] In the hydraulic composition of the present invention, the mass percentage of water content to hydraulic powder content (water / hydraulic powder ratio (W / P)) is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of further improving the uniformity of the coating film. Alternatively, the mass percentage (water / hydraulic powder ratio (W / P)) is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 45% by mass or less, from the viewpoint of further improving the uniformity of the coating film. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated as (water / hydraulic powder) × 100. The water / hydraulic powder ratio is calculated based on the amount of powder that has the physical properties to harden through a hydration reaction. Also, if the hydraulic powder is cement, W / P may be expressed as W / C. Furthermore, if the hydraulic powder includes powders selected from those having properties that harden through hydration reactions such as cement, powders having pozzolanic properties, powders having latent hydraulic properties, and stone powder (calcium carbonate powder), then in this invention, the amounts of these powders are also included in the amount of hydraulic powder. In addition, if the powder having properties that harden through hydration reactions contains a high-strength admixture, then the amount of the high-strength admixture is also included in the amount of hydraulic powder. This also applies to other parts of mass related to the mass of the hydraulic powder.

[0081] In the hydraulic composition of the present invention, the mass percentage of the hydraulic powder content to the aggregate content is preferably 60% by mass or less, more preferably 45% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of further improving workability during concrete placement, and from the viewpoint of further improving durability, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The mass percentage of the hydraulic powder content to the aggregate content is calculated as (hydraulic powder content / aggregate content) × 100.

[0082] Aggregates may be used within the normal range used in the preparation of concrete, mortar, etc. When the hydraulic composition is concrete, the amount of coarse aggregate used is preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less, from the viewpoint of the properties of the concrete. The bulk volume is 1 m³ of concrete. 3 This is the ratio of the volume of coarse aggregate (including voids) inside. Furthermore, when the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m³ from the viewpoint of further enhancing durability. 3 Above, a comfortable 600 kg / m 3 More preferably 700 kg / m 3 In addition, preferably 1,000 kg / m 3 More preferably 900 kg / m 3 The following applies: Furthermore, when the hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg / m³. 3 In summary, a comfortable 900 kg / m 3 More preferably, 1,000 kg / m 3 In addition, preferably 2,000 kg / m 3 More preferably, 1,800 kg / m 3 More preferably, 1,700 kg / m 3 The following applies:

[0083] The hydraulic composition of the present invention may optionally contain other components in addition to the above-mentioned components. Examples of other components include retarders, thickeners, air-entraining agents, waterproofing agents, fluidizing agents, rapid strengthening agents, defoaming agents, compatibilizers, preservatives, etc. (except for those corresponding to components (A) to (B) above). Examples of rapid strengthening agents include compounds selected from alkali metal or alkaline earth metal hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates; organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives; and nanoparticles of Portland cement hydration products (CSH, calcium carbonate, and calcium hydroxide).

[0084] The hydraulic composition of the present invention may use concrete or mortar. The hydraulic composition of the present invention is useful in any of the following fields, for example, self-leveling, refractories, plasters, lightweight or heavy concrete, air entrainment, repair, pre-packed materials, tremies, ground improvement, grouting, and cold weather applications.

[0085] [Method for producing a hydraulic composition] In an exemplary embodiment, the present invention provides a method for producing a hydraulic composition, which involves applying a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound [component (A)], (B) a plasticizer [component (B)], and (C) water [component (C)] to the surface of a mixture of hydraulic powder and water. The present invention may be a method for producing a hydraulic composition, in which a coating composition containing component (A), component (B), and component (C) is sprayed or applied to the surface of a mixture of hydraulic powder and water. In the method for producing the hydraulic composition of the present invention, the coating composition may optionally contain (D) a neutralizing agent [which is component (D)]. Furthermore, the method for producing the hydraulic composition of the present invention allows for the mixing of aggregate with the hydraulic powder.

[0086] In this specification, "applying a coating composition to a surface" means performing one or more of the following treatments: applying the coating composition to the surface of a cured structure, applying it to the surface of a molded body before curing, or applying it to a surface layer during the formation of a structure.

[0087] Specific examples and preferred embodiments of components (A), (B), (C), and (D) used in the method for producing the hydraulic composition of the present invention are the same as those described in the coating composition of the present invention, and specific examples and preferred embodiments of hydraulic powder and aggregate are the same as those described in the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the hydraulic powder is mixed such that the W / P ratio is within the range described in the hydraulic composition of the present invention. Furthermore, the amount of aggregate used (mixing amount) and the mass percentage of the hydraulic powder content to the aggregate content are also within the range described in the hydraulic composition of the present invention. The matters described in the present invention concerning the coating composition, its manufacturing method, and hydraulic composition can be applied to the manufacturing method of the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the content of each component and their mass ratio described in the hydraulic composition of the present invention can be applied by replacing the content of each component with the amount of mixture.

[0088] The method for producing the hydraulic composition of the present invention may be a method for producing a hydraulic composition which involves mixing hydraulic powder with water to obtain a hydraulic composition, and then spraying or coating the surface of the hydraulic composition with the coating composition of the present invention. In addition, the method for producing the hydraulic composition of the present invention preferably involves applying a coating composition containing component (A), component (B), and component (C) to the surface of the hydraulic composition and curing the hydraulic composition.

[0089] In the method for producing the hydraulic composition of the present invention, the coating composition comprising component (A), component (B), and component (C), and furthermore, the coating composition of the present invention, is preferably 100 g / m² from the viewpoint of further enhancing water repellency and UV resistance. 2 Above, a comfortable 150g / m 2 In addition to the above, and from the standpoint of labor costs, a preferable 250g / m² is preferred. 2 More preferably 200g / m² 2 The following amounts are applied to adhere the hydraulic composition to the surface. Alternatively, the coating amount is preferably 100 g / m² from the viewpoint of further enhancing water repellency and UV resistance, as well as from the viewpoint of labor costs. 2 More than 250g / m 2 More preferably, 150 g / m² 2 More than 200g / m 2 The following applies:

[0090] In the method for producing the hydraulic composition of the present invention, a coating composition containing component (A), component (B), and component (C), and a method for adhering the coating composition of the present invention to the surface of the hydraulic composition, include, for example, spraying, coating, or atomizing. Specifically, this includes coating the surface of the hydraulic composition with a brush or mop, spraying, or atomizing.

[0091] As a method for producing the hydraulic composition of the present invention, the hydraulic composition and water may be mixed using a mixer such as a mortar mixer or a forced twin-screw mixer. The mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, and more preferably 3 minutes or less.

[0092] The method for producing the hydraulic composition of the present invention may include, for example, a step of filling a mold with a mixture obtained by mixing hydraulic powder and water to obtain a molded body of the hydraulic composition, and then spraying or applying a coating composition containing components (A), (B), and (C), preferably the coating composition of the present invention, to the exposed surface of the molded body and curing it. Examples of molds used in the method for producing the hydraulic composition of the present invention include building molds and concrete product molds. Examples of methods for filling the mold include directly pouring the composition from a mixer and introducing the hydraulic composition into the mold by pumping it.

[0093] In the method for producing the hydraulic composition of the present invention, for example, when filling a mold with the hydraulic composition of the present invention and curing it, the hardening can be accelerated by heat curing. Here, heat curing may be, for example, by holding the hydraulic composition at a temperature of 40°C to 80°C to accelerate the hardening.

[0094] The hardened hydraulic composition can be demolded to obtain a hardened body of the hydraulic composition of the present invention. It is preferable that the hardened body of the hydraulic composition has sufficient compressive strength upon demolding. The compressive strength upon demolding is preferably equal to or greater than the strength specified in, for example, "Commentary Table 8.8.1 of the Japan Society of Civil Engineers Standard Specifications [Construction Edition] 2023."

[0095] Examples of hardened hydraulic compositions using concrete product formwork include, for civil engineering products, concrete piles, concrete poles, various block products for revetments, box culvert products, segment products used in tunnel construction, bridge pier girders, etc., and for architectural products, curtain wall products, columns, beams, and building components used in floor slabs, etc.

[0096] In the present invention, the time from contacting the hydraulic powder with water to demolding in the preparation of the hydraulic composition is preferably, for example, 16 hours or more and 72 hours or less, from the viewpoint of obtaining the strength necessary for demolding and improving the manufacturing cycle.

[0097] <Method for forming a coating layer> In exemplary embodiments, the present invention provides a method for forming a coating layer, comprising applying a coating composition to one or more surfaces selected from hydraulic composition surfaces and metal surfaces, the composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound [component (A)], (B) a plasticizer [component (B)], and (C) water [component (C)]. The present invention may provide a method for forming a coating layer, which includes spraying or applying a coating composition containing component (A), component (B), and component (C) to one or more surfaces selected from a hydraulic composition surface and a metal surface. In the method for forming a coating layer of the present invention, the coating composition may further optionally contain (D) a neutralizing agent [which is component (D)].

[0098] Specific examples and preferred embodiments of components (A), (B), (C), and (D) used in the method for forming the coating layer of the present invention are the same as those described in the coating composition of the present invention, and specific examples and preferred embodiments of the hydraulic composition, such as hydraulic powder and aggregate, are the same as those described in the hydraulic composition of the present invention. In the method for forming a coating layer of the present invention, the hydraulic powder is mixed such that the W / P ratio is within the range described in the hydraulic composition of the present invention. Furthermore, the amount of aggregate used (mixing amount) and the mass percentage of the hydraulic powder content to the aggregate content are also within the same range as described in the hydraulic composition of the present invention. In the method for forming a coating layer of the present invention, the content and mass ratio of each component described in the hydraulic composition of the present invention can be applied. The matters described in the coating composition and its manufacturing method, the coating composition, and the hydraulic composition and its manufacturing method of the present invention can be applied to the method for forming a coating layer of the present invention.

[0099] In the method for forming a coating layer of the present invention, the method for preparing the hydraulic composition may be the same as that described in the method for producing the hydraulic composition of the present invention.

[0100] The method for forming a coating layer according to the present invention makes it possible to form a film with excellent water repellency and excellent ultraviolet resistance on a surface selected from the surface of a hydraulic composition and a metal surface, as well as on the surface of a hardened hydraulic composition. In other words, the method for forming a coating layer according to the present invention may be a method for forming a hydrophobic coating layer. [Examples]

[0101] The components used to prepare the coating compositions for the examples and comparative examples are shown below. <(A) component> • A-1: ​​Polymer produced in Manufacturing Example 1 below • A-2: Polymer produced in manufacturing example 2 below • A-3: Polymer manufactured in manufacturing example 3 below • A-4: Polymer produced in manufacturing example 4 below <(A') component> • A'-1: Polymer produced in manufacturing example 5 below • A'-2: Polymer produced in manufacturing example 6 below

[0102] <(B) component> • B-1: Diallyl phthalate, molecular weight 246.3, specific gravity 1.121 g / mL (25℃), manufactured by Fujifilm Wako Pure Chemical Corporation. B-2: Tributyl acetylcitrate, molecular weight 402.5, specific gravity 1.05 g / mL (25℃), manufactured by Fujifilm Wako Pure Chemical Corporation. • B-3: Oleic acid (2-ethylhexyl), molecular weight 394.67, specific gravity 0.866~0.873 g / mL (20℃), manufactured by Kao Corporation.

[0103] <(C) component> ·water <(D) component> D-1: DMAE, Dimethylaminoethanol D-2: KOH, potassium hydroxide D-3: NH3, ammonia <(E) component> • E-1: Methyl ethyl ketone

[0104] <(A) Method for manufacturing component> Polyester components A-1 to A-4 and comparative components A'-1 to A'-2 of component (A) were produced according to the manufacturing methods described in Manufacturing Examples 1 to 6 below. Table 1 shows the monomer composition and physical properties of each component. The values ​​in the table represent the amount of active ingredient.

[0105] [Table 1]

[0106] (1) Manufacturing Example 1 (Manufacturing of Polyester A-1) The alcohol, terephthalic acid, and polyethylene terephthalate (UNIFI, 100% Post ConsumerrPETResin / 500 Mesh Filtered / Round / Bright / 0.68IV / Crystallized) shown in Table 1 were placed in a 5-liter four-necked flask equipped with a thermometer, thermocouple, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube, and heated to 120°C. The esterification catalyst shown in Table 1 was then added at 120°C, and the temperature was rapidly increased to 235°C. After reaching 235°C, the temperature was maintained for 4 hours while the reaction system was thoroughly stirred. After 4 hours of reaction, the temperature was reduced to 185°C, and then dodecenyl succinic anhydride was added. The temperature was increased to 220°C at 10°C / 30 minutes, and then the reaction was carried out at 220°C and 100 torr for approximately 2 hours until the softening point shown in Table 1 was reached, thereby producing polyester A-1.

[0107] (2) Manufacturing Examples 2 and 3 (Manufacturing of Polyester A-2 and A-3) Polyester A-2 and A-3 were manufactured using the same method as in Manufacturing Example 1, except that the amount of polyester raw material was changed as shown in Table 1.

[0108] (3) Manufacturing Example 4 (Manufacturing of Polyester A-4) Polyester A-4 was produced in the same manner as in Production Example 1, except that polyethylene terephthalate was added at the stage before the start of the reduced pressure reaction at 220°C and 100 torr, rather than before heating at 120°C as in Production Example 1, and then reacted at 220°C and 100 torr for approximately 3 hours.

[0109] (4) Manufacturing Example 5 (Manufacturing of Polyester A'-1) The components shown in Table 1 were placed in a 5-liter four-necked flask equipped with a thermometer, thermocouple, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube. The esterification catalyst shown in Table 1 was added under a nitrogen atmosphere, and the temperature was raised to 215°C over 3 hours. After reaching 215°C, the temperature was maintained for 5 hours. Subsequently, a reduced-pressure reaction was carried out at 8.0 kPa for 1 hour until the softening point shown in Table 1 was reached, thereby producing polyester A'-1.

[0110] (5) Manufacturing Example 6 (Manufacturing of Polyester A'-2) The polyoxypropylene adduct of bisphenol A, the polyoxyethylene adduct of bisphenol A, terephthalic acid, and dodecenyl succinic anhydride shown in Table 1 were placed in a 5-liter four-necked flask equipped with a stainless steel stirring rod, a drop-through condenser, and a nitrogen inlet tube. 25 g of tin(II) di(2-ethylhexanoate) and 2 g of gallic acid (esterification co-catalyst) were added under a nitrogen atmosphere, and the mixture was heated to 235°C over 3 hours, where it was maintained for 5 hours. After that, a reduced-pressure reaction was carried out at 8.0 kPa for 1 hour, followed by cooling to 210°C. Trimellitic anhydride was added at 210°C, maintained at 210°C for 1 hour, and then a reduced-pressure reaction was carried out at 8.0 kPa. The reaction was continued until the softening point shown in Table 1 was reached, yielding polyester A'-2.

[0111] (6) Method for measuring the softening point and glass transition point of polyester (i) Softening point Using a flow tester (Shimadzu Corporation, "CFT-500D"), 1 g of sample was heated at a heating rate of 6°C / min while a load of 1.96 MPa was applied by a plunger and extruded through a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was defined as the softening point. (ii) glass transition temperature Using a differential scanning calorimeter (TA Instruments Japan Co., Ltd., "Q-100"), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then cooled to 0°C at a rate of 10°C / min. Next, the heat quantity was measured while heating to 150°C at a rate of 10°C / min. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rise of the peak to the peak apex was defined as the glass transition point.

[0112] (7) Method for measuring the acid value and hydroxyl value of polyester The acid value and hydroxyl value of the polyester were measured according to the method of JIS K 0070:1992. However, the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070:1992 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[0113] (8) Differential scanning calorimetry: Method for measuring heat generation at temperatures between 240°C and 260°C Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan and heated to 300°C at a heating rate of 10°C / min. A baseline was drawn over the portion of the exothermic behavior that included the maximum peak temperature of exothermic reaction, and the area of ​​this baseline was defined as the amount of heat generated.

[0114] <Method for producing coating compositions> Coating compositions Em-1 to Em-8 and em-1 to em-2 were prepared according to the manufacturing methods for the coating compositions Em-1 to Em-8 and em-1 to em-2 described below, each containing components (A), (B), (C), and (D) listed in Table 2. The values ​​in the table represent the amount of active ingredient.

[0115] (1) Method for producing coating composition Em-1 400 g of (E) methyl ethyl ketone and 400 g of (A) polyester A-1 were placed in a 5-liter three-necked flask equipped with a reflux tubing, stirrer, and thermocouple. The mixture was heated to 60°C while stirring at 200 rpm until polyester A-1 was completely dissolved in (E) methyl ethyl ketone. The resulting polyester A-1 solution was cooled to 50°C, and 80 g of (B) diallyl phthalate and 9.1 g of (D) dimethylaminoethanol were added. Then, 800 g of (C) water at 50°C was added while stirring. Subsequently, a distillation tube and trap were placed in a 5-liter container to allow for the distillation of (E) methyl ethyl ketone. The mixture was then reduced to 80-150 torr using a vacuum pump at 40°C and distilled off until the concentration of (E) methyl ethyl ketone was 100 ppm or less. Finally, the mixture was filtered through a 150-mesh wire mesh to produce an aqueous emulsion of polyester A-1, which is the coating composition Em-1. The solid content of the obtained emulsion was measured using the method described in (11) below for measuring the solid content of emulsions. The average particle size of polyester in the emulsion was measured using the method described in (12) below for measuring the average particle size. The results are shown in Table 2.

[0116] (2) Method for producing coating composition Em-2 (D) An aqueous emulsion of polyester A-1, which is coating composition Em-2, was produced in the same manner as the production method for coating composition Em-1, except that the neutralizing agent was changed from dimethylaminoethanol to potassium hydroxide and 35.6 g of a 10% potassium hydroxide aqueous solution was added as the neutralizing agent (D).

[0117] (3) Method for producing coating composition Em-3 (B) The amount of diallyl phthalate added was 48 g, and (D) the amount of dimethylaminoethanol added was 16.4 g, in addition to producing a water-based emulsion of polyester A-1, which is coating composition Em-3, in the same manner as the production method for coating composition Em-1.

[0118] (4) Method for producing coating composition Em-4 (B) An aqueous emulsion of polyester A-1, which is coating composition Em-4, was produced in the same manner as the method for producing coating composition Em-1, except that the plasticizer was changed from diallyl phthalate to tributyl acetylcitrate.

[0119] (5) Method for producing coating composition Em-5 (B) Except for changing the plasticizer from diallyl phthalate to 2-ethylhexyl oleate, an aqueous emulsion of polyester A-1, which is coating composition Em-5, was produced in the same manner as the method for producing coating composition Em-1.

[0120] (6) Method for producing coating composition Em-6 Except for (A) changing the polyester from A-1 to A-2 and (D) changing the amount of dimethylaminoethanol added to 4.12 g, an aqueous emulsion of polyester A-2, which is coating composition Em-6, was produced in the same manner as the production method for coating composition Em-1.

[0121] (7) Method for producing coating composition Em-7 Except for (A) changing the polyester from A-1 to A-3 and (D) changing the amount of dimethylaminoethanol added to 9.40 g, an aqueous emulsion of polyester A-3, which is coating composition Em-7, was produced in the same manner as the production method for coating composition Em-1.

[0122] (8) Method for producing coating composition Em-8 Except for (A) changing the polyester from A-1 to A-4 and (D) changing the amount of dimethylaminoethanol added to 10.3 g, an aqueous emulsion of polyester A-4, which is coating composition Em-8, was produced in the same manner as the production method for coating composition Em-1.

[0123] (9) Method for producing coating composition em-1 Except for (A) changing the polyester from A-1 to A'-1 and (D) changing the amount of dimethylaminoethanol added to 10.7 g, an aqueous emulsion of polyester A'-1, which is the coating composition em-1, was produced in the same manner as the production method for coating composition Em-1.

[0124] (10) Method for producing coating composition em-2 In a 5-liter container equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet tube, 500 g of (A') polyester A'-2 and 500 g of (E) methyl ethyl ketone were placed, and the polyester was dissolved at 60°C for 3 hours. After cooling to 35°C, 100 g of (B) tributyl acetyl citrate and 6.67 g of (D) 25% by mass aqueous ammonia were added to the solution and stirred for 60 minutes. Then, while maintaining the temperature at 35°C and stirring at 200 rpm, 1082 g of (C) deionized water was added over 120 minutes to induce phase inversion emulsification. After heating to 60°C, (E) methyl ethyl ketone was removed by distillation under reduced pressure to obtain an aqueous dispersion. After cooling the aqueous dispersion to 30°C while stirring, (C) deionized water was added to adjust the solid content concentration to approximately 40% by mass. The mixture was then filtered through a 150-mesh wire mesh to produce an aqueous emulsion of polyester A'-2, which is the coating composition em-2.

[0125] (11) Method for measuring the solid content of emulsions Using an infrared moisture meter (FD-230, manufactured by Kett Scientific Research Institute Co., Ltd.), 5 g of the sample was dried at a drying temperature of 150°C and measurement mode 96 (monitoring time 2.5 minutes, variation range 0.05%), and the moisture content (mass %) of the sample was measured. The solid content concentration was calculated according to the following formula. The results are shown in Table 2. Solid concentration (mass%) = 100-moisture (mass%)

[0126] (12) Method for measuring average particle size (i) Measuring device: Laser diffraction particle size analyzer "LA-960" (manufactured by Horiba, Ltd.) (ii) Measurement method: Deionized water, which is the dispersion medium, was added to the measurement cell, and the sample was added in small amounts. The volume median particle size (D50) was measured when the amount of sample was such that the transmittance of red light (transmittance (R)) and the transmittance of blue light (transmittance (B)) were within the range shown in (v) below. The results are shown in Table 2. (iii) Device setting conditions (Measuring cell) Flow cell (Sample) LD Real term (Sample): 1.6 LD Imaginary term (Sample): 0 LED Real term (sample): 1.6 LED Imaginary term (sample): 0 (Dispersion medium) LD real term (dispersion medium): 1.333 LED real number term (dispersion medium): 1.333 (Measurement liquid) Ultrasonic: OFF Stirring: 2 Circulation: 5 (iv) Dispersion medium: Ion-exchanged water (v) Sample quantity: An amount that falls within the following transmittance range. Transmittance (R): 80~98% Transmittance (B): 60~90%

[0127] [Table 2]

[0128] <Method for manufacturing the coating composition> Using the coating compositions listed in Table 2, coating compositions were prepared, and their hydrophobicity and UV resistance were evaluated. Specifically, 5.0 g of the coating composition shown in Table 2 was placed in an aluminum cup and dried at 105°C for 2 hours to prepare a uniform coating composition.

[0129] <UV resistance evaluation> (1) Test method The obtained coating composition was placed in an accelerated weathering test apparatus (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.) and tested under conditions of 40°C and 75% RH, with wavelengths of 300nm to 400nm and a power of 150W / m². 2 The sample was exposed to ultraviolet light for 12 hours. The glass transition temperature Tg (°C) was measured and suggested scanning calorimetry (DSC) measurements were performed on both the coating composition before and after irradiation with ultraviolet light, using the method described below. The results are shown in Table 3. Samples in which the change in glass transition temperature (Tg) is small between the coating composition before irradiation with ultraviolet light and the coating composition after irradiation with ultraviolet light are samples that show little degradation due to exposure to ultraviolet light and are coating compositions with excellent UV resistance.

[0130] (2) Method for measuring the glass transition temperature Tg of a coating composition Using a differential scanning calorimeter "Q100" (manufactured by T.A. Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the coating composition was weighed into an aluminum pan, heated from room temperature to 150°C at a rate of 10°C / min, cooled from that temperature to -50°C at a rate of 10°C / min, and then heated again to 150°C at a rate of 10°C / min, and the amount of heat was measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the peak apex was defined as the glass transition point.

[0131] <Method for evaluating hydrophobicity> The hydrophobicity was evaluated on the coating composition before and after irradiation with ultraviolet light, as in the UV resistance evaluation described above. Specifically, the diameter of the water droplet was measured when 35 mg of distilled water was dropped onto the coating composition from a height of 2 cm using a 3 mm dropper. Three water droplets were arbitrarily selected, and the average value was calculated. The results are shown in Table 3. The smaller the water droplet diameter, the higher the hydrophobicity of the coating composition and the better its water-repellent properties. Furthermore, the change in water droplet diameter was calculated for the coating composition before and after irradiation with ultraviolet light. The results are shown in Table 3. Samples with a small change in diameter are those that show little degradation due to exposure to ultraviolet light and are coating compositions with excellent water repellency and UV resistance. Furthermore, the percentage change in water droplet diameter before and after UV light irradiation was calculated using the following formula (1). The results are shown in Table 3. The smaller the percentage change in water droplet diameter, the less degradation the sample undergoes due to UV light exposure, and the more the coating composition exhibits excellent water repellency and UV resistance. The percentage change in water droplet diameter before and after irradiation (%) = [(Water droplet diameter determined for the coating composition after UV irradiation) - (Water droplet diameter determined for the coating composition before UV irradiation)] / (Water droplet diameter determined for the coating composition before UV irradiation)] × 100 (1)

[0132] The smaller the water droplet diameter measured on the coating composition after UV irradiation, the better the UV resistance and the superior the water repellency of the coating composition. Therefore, the hydrophobicity of the coating composition was evaluated according to the following hydrophobicity evaluation criteria. The results are shown in Table 3. The coating compositions are evaluated in the order of A, B, C, and D, from highest to lowest hydrophobicity. <Evaluation Criteria for Hydrophobicity> A: The water droplet diameter measured on the coating composition after UV irradiation is small, and the change in water droplet diameter measured before and after UV irradiation is small. B: The water droplet diameter measured on the coating composition after UV irradiation was slightly smaller, and the change in water droplet diameter measured before and after UV irradiation was small. C: The water droplet diameter measured with the coating composition before UV irradiation was slightly smaller, but it became slightly larger after UV irradiation. D: The water droplet diameter measured on the coating composition after UV irradiation is large.

[0133] As shown in Table 3, by applying the coating compositions shown in Table 2 to the hydraulic composition, a hydraulic composition having a coating layer with excellent water repellency and excellent UV resistance can be obtained.

[0134] Table 3

Claims

1. A coating composition comprising (A) polyester, (B) a plasticizer, and (C) water, wherein component (A) comprises a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound.

2. The coating composition according to claim 1, wherein the heat generated by the component (A) in differential scanning calorimetry at 240°C to 260°C is 10 J / g or less.

3. The coating composition according to claim 1 or 2, wherein the polyethylene terephthalate is recycled polyethylene terephthalate.

4. The coating composition according to claim 1 or 2, wherein the specific gravity of component (B) is 0.85 or more and 1.20 or less.

5. (D) The coating composition according to claim 1 or 2, comprising a neutralizing agent.

6. The coating composition according to claim 5, wherein component (D) is one or more selected from alkali metal hydroxides, ammonia, alkylamines, and alkylalkanolamine nitrogen-containing basic substances.

7. The coating composition according to claim 1 or 2, wherein the glass transition temperature of the solid obtained by drying the coating composition is -20°C or higher and 30°C or lower.

8. The coating composition according to claim 1 or 2, wherein the alcohol from which the constituent units of component (A) are derived includes an alkylene oxide adduct of bisphenol A.

9. The coating composition according to claim 8, wherein the content of constituent units derived from the alkylene oxide adduct of bisphenol A is 20 mol% or more and 95 mol% or less out of 100 mol% of constituent units derived from the alcohol constituting the polyester of component (A).

10. The coating composition according to claim 1 or 2, wherein the content of constituent units consisting of polyethylene terephthalate, ethylene glycol, and terephthalic acid in component (A) is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of constituent units of component (A).

11. The coating composition according to claim 1 or 2, wherein the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is 0.05 or more and 0.3 or less.

12. A method for producing a coating composition, comprising mixing (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

13. Furthermore, the method for producing the coating composition according to claim 12, comprising (D) mixing in a neutralizing agent.

14. A coating composition formed from a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

15. A hydraulic composition comprising a hardened body of a hydraulic composition and a coating layer provided on the surface of the hydraulic composition, wherein the coating layer is formed from a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water.

16. A method for producing a hydraulic composition, comprising applying a coating composition containing (A) a polyester comprising a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water to the surface of a mixture of hydraulic powder and water.

17. A method for forming a coating layer, comprising applying a coating composition comprising (A) a polyester containing a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, (B) a plasticizer, and (C) water to one or more surfaces selected from a hydraulic composition surface and a metal surface.

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