JP2023013598A - Coating composition, and, coating agent for covering concrete structure using the coating composition, and coating method for coating agent for covering concrete structure - Google Patents

Abstract

To provide a coating composition that allows confirmation of the coating state during coating, and is excellent in base visibility, adhesion, and wet skin prevention after coating film formation, and to provide a coating agent for covering concrete structure using the composition, and coating method for coating agent for covering concrete structure.SOLUTION: Provided is a coating composition that contains at least a non-radical-reactive aqueous emulsion (A), colloidal silica (B), a radical generator (C), and a radical-reactive dye (D).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a coating composition, a coating agent for covering concrete structures using the composition, and a coating method for the coating agent for covering concrete structures.

Conventionally, structures using cement such as concrete and mortar are materials with excellent durability. It is known that cracks occur on the surface. Cracks on the surface of concrete or the like affect its durability. For this reason, in order to confirm the degree of deterioration in durability of concrete or the like, the degree of crack generation is often visually observed.

On the other hand, various techniques have been proposed as techniques for preventing deterioration of concrete and the like. For example, for the purpose of preventing drying and suppressing water absorption, and in addition to imparting waterproofness, water repellency, abrasion resistance, etc., for various purposes such as aesthetics, the technique of coating the surface of concrete etc. with a single or multiple layers is known. (See Patent Documents 1 to 4 below, for example).

JP-A-2-13338 JP-A-2002-316883 Japanese Patent Application Laid-Open No. 2004-314328 JP 2013-081937 A

However, when the surface of concrete, etc. is coated with a coating agent as in the above technology, the color of the concrete surface changes due to reasons such as coloring by the coating agent and impregnation of the coating agent, and the concrete surface turns black as if wet. , so-called "wet skin" may occur. In this way, wet texture, that is, when the color of the concrete surface changes, there is a problem that the visibility is lowered when the concrete surface is visually checked, making it difficult to find cracks and the like.

On the other hand, in order to suppress deterioration of the visibility of the concrete surface, it may be possible to use a coating agent that becomes colorless and transparent when formed into a coating film. However, if the coating film is colorless and transparent, it is difficult to visually confirm whether or not the coating film is uniformly formed on the concrete surface after the coating film is applied, and the coating film becomes uneven. It becomes difficult to visually confirm whether or not the

In order to solve the above-mentioned problems, the present invention provides a coating composition that allows confirmation of the coating state during coating, and has excellent base visibility, adhesion, and wet skin prevention after coating film formation. It is also an object of the present invention to provide a coating agent for covering concrete structures using the composition, and a coating method for the coating agent for covering concrete structures.

（式中、Ｒ¹～Ｒ⁶は、各々独立して、水素、ハロゲンを有していてもよい、炭素数１～４のアルキル基、及び、炭素数２～４のアルケニル基を示す。式中、ＨＸは、Ｘが、Ｃｌ、Ｂｒ、Ｉ、Ｆから選択されるモノプロトン酸を示す。）
［５］
前記ラジカル反応性色素（Ｄ）が、可視・紫外分光光度計の測定において、熱及び／又は光照射前の４００～８００ｎｍの範囲における極大値を示す波長の吸光度が、熱及び／又は光照射後に０．５ａｂｓ以下となる、前記［１］～前記［４］のいずれか一つに記載のコーティング組成物。
［６］
前記［１］～前記［５］のいずれか一つに記載のコーティング組成物を含む、コンクリート構造物被覆用コーティング剤。
［７］
前記［６］に記載のコンクリート構造物被覆用コーティング剤をコンクリート基材に付与して塗膜を形成する工程と、
前記コンクリート基材に付与された前記コンクリート構造物被覆用コーティング剤の少なくとも一部に熱及び／又は光を照射して前記コンクリート構造物被覆用コーティング剤を無色透明化する工程と、を含む、
コンクリート構造物被覆用コーティング剤の塗装工法。
［８］
土木学会規格 ＪＳＣＥ Ｋ－５３１－２０１３）「連続繊維補強材の引張試験方法」に準拠した付着性試験において、前記コンクリート基材と前記塗膜との付着強度が、１Ｎ／ｍｍ²以上である、前記［７］に記載の塗装工法。
［９］
ＮＥＸＣＯ規格 試験法４２５－２００４「はく落防止の耐久性能試験方法」に準拠した塩化物イオン透過性の試験において、ＪＩＳ Ｋ０１０１の塩化物イオンの分析方法によって測定した塩素イオン濃度を使用し、下記式（１）から算出した前記塗膜の塩化物イオン透過度が、０．００５ｇ／ｍ²・ｄａｙ以下である、前記［７］に記載の塗装工法。

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ²・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ²）〕
［１０］
ＪＩＳ Ａ１１５３：２０１２に規定される「コンクリートの促進中性化試験方法」に準拠した中性化阻止性の試験において、温度３０℃、相対湿度６０％、二酸化炭素濃度５%の環境槽内に２８日間静止後の前記塗膜の中性化深さが、１ｍｍ以下である、前記［７］に記載の塗装工法。 [1]
at least,
a non-radical reactive aqueous emulsion (A);
colloidal silica (B);
a radical generator (C);
a radical-reactive dye (D);
A coating composition containing
[2]
The coating composition according to the above [1], wherein the radical-reactive dye (D) contains a compound containing a tetraterpene structure.
[3]
The coating composition according to [2] above, wherein the compound containing a tetraterpene structure is at least one selected from cartenoid dyes and xanthophyll dyes.
[4]
Any one of [1] to [3] above, wherein the radical-reactive dye (D) comprises a phenothiazine derivative containing a 3,7-diamino-10H-phenothiazine structure represented by the following general formula (1): The coating composition according to .

(In the formula, R ¹ to R ⁶ each independently represent hydrogen, an optionally halogenated alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. In the middle, HX denotes a monoprotonic acid in which X is selected from Cl, Br, I, and F.)
[5]
The radical-reactive dye (D) exhibits a maximum absorbance at a wavelength in the range of 400 to 800 nm before heat and/or light irradiation, in measurement with a visible/ultraviolet spectrophotometer, after heat and/or light irradiation. The coating composition according to any one of [1] to [4], which is 0.5 abs or less.
[6]
A coating agent for covering a concrete structure, comprising the coating composition according to any one of [1] to [5].
[7]
A step of applying the coating agent for covering a concrete structure according to the above [6] to a concrete base material to form a coating film;
a step of irradiating at least part of the concrete structure coating agent applied to the concrete base material with heat and/or light to make the concrete structure coating agent colorless and transparent;
A coating method for a coating agent for covering concrete structures.
[8]
In an adhesion test conforming to the Japan Society of Civil Engineers standard JSCE K-531-2013) "Tensile test method for continuous fiber reinforcement", the adhesion strength between the concrete base material and the coating film is 1 N / mm ² or more. The coating method according to [7] above.
[9]
In a chloride ion permeability test in accordance with NEXCO Standard Test Method 425-2004 "Durability test method for preventing flaking", the chloride ion concentration measured by the chloride ion analysis method of JIS K0101 was used, and the following formula ( The coating method according to [7] above, wherein the chloride ion permeability of the coating film calculated from 1) is 0.005 g/m ² ·day or less.

[Cl: chloride ion permeability (g/m ² ·day), V: amount of deionized water in the cell (ml), M: chloride ion concentration (mg/l), A: chloride ion permeation area (cm ² )]
[10]
In the test of neutralization resistance in accordance with the "test method for accelerated neutralization of concrete" specified in JIS A1153:2012, 28 The coating method according to the above [7], wherein the neutralization depth of the coating film after resting for a day is 1 mm or less.

According to the present invention, a coating composition that allows confirmation of the coating state during coating and has excellent base visibility, adhesion, and wet skin prevention after coating film formation, and the composition It is possible to provide a coating agent for coating concrete structures using and a coating method for coating agents for coating concrete structures.

<<Coating composition>>
The coating composition of the present embodiment (hereinafter sometimes simply referred to as "coating composition") comprises at least a non-radical reactive aqueous emulsion (A), colloidal silica (B), and a radical generator (C) and a radical-reactive dye (D). The coating composition may also contain other materials as needed.

The coating composition of the present embodiment can be suitably used as a coating agent for coating concrete structures. And it is excellent in wet skin prevention property. Here, "concrete" mainly means a mixture of cement mixed with water, fine aggregate such as sand, and coarse aggregate such as gravel. Also, "mortar" mainly means a mixture of cement mixed with water and fine aggregate. "Cement" is obtained by firing limestone, clay, silica, iron raw materials, etc. that have been dried, crushed, and mixed at high temperatures, quenching them, adding gypsum, and pulverizing them. As used herein, the term "concrete surface" includes not only the surface of concrete but also the surface of structures formed of a mixture containing cement such as mortar.

First, according to the present embodiment, the colloidal silica (B) closes the micropores in the porous structure of the concrete surface, so that the coating composition containing the non-radical-reactive aqueous emulsion (A) becomes porous on the concrete surface. Since it can be prevented from penetrating deeply into the structure, when used as a coating agent for covering concrete structures, it has excellent adhesion between the concrete surface and the coating film. In addition, since the colloidal silica (B) acts to allow the coating composition to stay near the concrete surface, the barrier effect prevents neutralization due to the influence of carbon dioxide and chlorides in the air, and chlorides adhering to the surface. It is possible to effectively suppress the intrusion of material ions and the like into the concrete, thereby improving the durability of the concrete.

In addition, since the coating composition of the present embodiment contains a radical-reactive dye (D), when a coating film is formed on a concrete surface, occurrence of uneven coating of the coating composition can be visually confirmed. . Therefore, according to the coating agent of the present embodiment, the state of application to the concrete surface can be easily confirmed by visual inspection, for example.
Furthermore, the coating agent of the present embodiment contains a radical-reactive dye (D) and a radical generator (C) that fade by reaction with radical species, and further uses a non-radical-reactive aqueous emulsion (A). Therefore, the fading reaction of the radical-reactive dye (D) is efficiently promoted by the radical species generated by the decomposition of the radical generator (C), etc., without being inhibited by the aqueous emulsion, and the coating film is faded, preferably Can be colorless and transparent. Therefore, when the coating composition of the present embodiment is used as a coating agent for covering a concrete structure, the base visibility after forming the coating film is excellent.

In addition, the coating composition is effective in concrete due to the combined effect of the non-radical-reactive aqueous emulsion (A) and the colloidal silica (B), and the fading of the radical-reactive dye (D) after the formation of the coating film. It is possible to suppress the surface from becoming wet skin-like. Furthermore, the coating composition of the present embodiment has excellent wet skin prevention properties and base visibility, so after construction, the degree of deterioration of the durability of concrete, etc., such as the occurrence of cracks, can be easily visually checked. can be observed.

<Non-Radical Reactive Aqueous Emulsion (A)>
The water-based emulsion that can be used as the non-radical-reactive water-based emulsion (A) is not particularly limited as long as it does not react with the radical species generated by the decomposition of the radical generator (C). Here, the "non-radical reactive aqueous emulsion" is preferably an aqueous emulsion that does not have a diene structure that reacts with radical species. Since the coating composition of the present embodiment uses an aqueous emulsion, it is excellent in environmental friendliness and handleability.
Moreover, it is preferable that the non-radical-reactive aqueous emulsion (A) can be formed into a film at room temperature (about 10° C. or higher). Therefore, the glass transition temperature of the non-radical reactive aqueous emulsion (A) is preferably -70 to 0°C, more preferably -40 to -10°C, from the viewpoint of film-forming properties and handling properties at room temperature. A glass transition temperature can be measured by a differential scanning calorimeter (DSC).
Moreover, the particle size of the non-radical-reactive aqueous emulsion (A) is preferably 1 μm or less, more preferably 1 to 100 nm, and more preferably 1 to 50 nm, from the viewpoint of further improving the effects of the present invention. The particle size can be measured by a laser diffraction scattering method.

Examples of the non-radical-reactive aqueous emulsion (A) include acrylic resins, urethane resins, urethane-modified resins, polyester resins, vinyl ester resins, phenol resins, and epoxy resins from the viewpoint of adhesion to concrete structures and durability. , melamine resin, olefin resin, silicone resin, etc., using an emulsifier, forcibly emulsified or emulsion polymerized to obtain a non-radical reactive aqueous emulsion.

(1) Acrylic resin As the acrylic resin that can be used as the non-radical-reactive aqueous emulsion (A), at least one (meth)acryloyl group-containing radically polymerizable unsaturated monomer is used to generate radicals in the present embodiment. Resins polymerized by energy such as ultraviolet rays, electron beams, heat, etc., using an initiator that promotes polymerization by radicals like the agent. Here, "(meth)acrylate" means "one or both of methacrylate and acrylate". Moreover, in this specification, "(meth)acryloyl group" means "one or both of an acryloyl group and a methacryloyl group".

-(Meth)acryloyl Group-Containing Radically Polymerizable Unsaturated Monomer-
Specific examples of the (meth)acryloyl group-containing radically polymerizable unsaturated monomer are not particularly limited, but methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, acrylic Hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, alkyl acrylates such as dodecyl acrylate, aryl acrylates such as phenyl acrylate and benzyl acrylate, methoxyethyl acrylate , alkoxyalkyl acrylates such as ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, and ethoxypropyl acrylate; salts such as acrylic acid and alkali metal acrylate salts; methacrylic acid and alkali metal methacrylate salts; salts, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, etc. Alkyl methacrylates, aryl methacrylates such as phenyl methacrylate and benzyl methacrylate, alkoxyalkyl methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate and ethoxypropyl methacrylate , ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate Esters such as (poly)alkylene glycol diacrylates, ethylene glycol dimethacrylates, diethylene glycol dimethacrylates, triethylene glycol dimethacrylates, polyethylene glycol diacrylates, propylene glycol dimethacrylates Dimethacrylates of (poly)alkylene glycols such as S-L, dimethacrylates of dipropylene glycol, and dimethacrylates of tripropylene glycol; Polyvalent acrylates such as tyrolpropane triacrylate, polyvalent methacrylates such as trimethylolpropane trimethacrylate, acrylonitrile, methacrylonitrile; vinyl acetate, vinylidene chloride, 2-chloroethyl acrylate, methacrylic acid -Vinyl halide compounds such as 2-chloroethyl, acrylic acid esters of alicyclic alcohols such as cyclohexyl acrylate, methacrylic acid esters of alicyclic alcohols such as cyclohexyl methacrylate, 2-vinyl-2-oxazoline, 2-vinyl -5-methyl-2-oxazoline, oxazoline group-containing polymerizable compounds such as 2-isopropenyl-2-oxazoline, acryloylaziridine, methacryloylaziridine, 2-aziridinylethyl acrylate, 2-aziridinyl methacrylate aziridine group-containing polymerizable compounds such as ethyl; Containing vinyl monomers, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, monoesters of acrylic acid or methacrylic acid and polypropylene glycol or polyethylene glycol, lactones hydroxyl group-containing vinyl compounds such as adducts of and (meth)acrylic acid-2-hydroxyethyl, fluorine-containing vinyl monomers such as fluorine-substituted methacrylic acid alkyl esters and fluorine-substituted acrylic acid alkyl esters, (meth)acrylic acid Unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid, fumaric acid, their salts, and their (partial) ester compounds and acid anhydrides, 2-chloroethyl vinyl ether, monochloro vinyl acetate, etc. halogen-containing vinyl monomers, amide group-containing vinyl monomers such as methacrylamide, N-methylol methacrylamide, N-methoxyethyl methacrylamide, N-butoxymethyl methacrylamide, vinyltrimethoxysilane, γ-methacryloxypropyl organosilicon group-containing vinyl compounds such as trimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane; Polymers, and macromonomers having a radically polymerizable vinyl group at the end of a monomer obtained by polymerizing a vinyl group (eg, fluorine-based monomers, silicone-containing monomers, macromonomers, styrene, silicone, etc.).

From the viewpoint of strength and durability, a radically polymerizable unsaturated monomer having two or more (meth)acryloyl groups in the molecule can be used in combination in the synthesis of the acrylic resin. Specific examples of radically polymerizable unsaturated monomers having two or more (meth)acryloyl groups in the molecule include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) Acrylates, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated bisphenol A di( meth)acrylate, tricyclodecane di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate ) acrylate, dipentaesritol poly(meth)acrylate, dipentaesritol hexa(meth)acrylate, 2,2-bis[4-(methacryloxyethoxy)phenyl]propane, 2,2-bis[4- (Methacryloxy-diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy-polyethoxy)phenyl]propane, 2,2-bis[4-(acryloxy-diethoxy)phenyl]propane, 2,2-bis[4 -(Acryloxy-polyethoxy)phenyl]propane and the like.

(2) Urethane resin The urethane resin that can be used as the non-radical-reactive aqueous emulsion (A) is a resin produced by polymerization of a compound having at least one active hydrogen group and an isocyanate compound.

[Active Hydrogen Group-Containing Compound]
Specific examples of the active hydrogen group-containing compound used in the urethane resin are not particularly limited as long as they have at least one or more active hydrogen groups and react with the isocyanate compound. For example, dimer polyol Polyester polyols, polyether polyols, polycarbonate polyols, acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, olefin polyols, and polythiol compounds containing at least polymers and low-molecular-weight polyols having active hydrogen groups 1 type is mentioned.

-Polyester polyol-
Specific examples of polyester polyols including dimer polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid. , azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, fumaric acid Dicarboxylic acids such as oleic acid and linoleic acid, dicarboxylic acids with 36 carbon atoms obtained by dimerizing unsaturated fatty acids with 18 carbon atoms, or one or more of these anhydrides, ethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8 -octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane- 1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. One or more of the molecular polyols and those obtained from the condensation polymerization reaction can be mentioned. Lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone can also be used. Furthermore, a polyester-amide polyol obtained by replacing part of the low-molecular-weight polyol with a low-molecular-weight polyamine such as hexamethylenediamine, isophoronediamine, or monoethanolamine or a low-molecular-weight aminoalcohol can also be used.

-Polyether Polyol-
Specific examples of polyether polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 - pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Low-molecular-weight polyols, or low-molecular-weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine. as an initiator, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, or alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, Polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as tetrahydrofuran can be mentioned.

-Polycarbonate polyol-
Specific examples of polycarbonate polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neo Pentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, One or more of low-molecular-weight polyols such as xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, and dinaphthyl Those obtained from dealcoholization reaction and dephenolation reaction with diaryl carbonates such as carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate can be mentioned.
A polyol obtained by transesterification reaction of a polycarbonate polyol, a polyester polyol and a low-molecular-weight polyol can also be used.

-Acrylic Polyol-
The acrylic polyol contains at least one hydroxyl group-containing acrylate compound in the molecule that can serve as a reaction site, and a (meth)acryloyl group-containing radically polymerizable unsaturated monomer and a polymerization initiator are combined with heat energy. Examples include polyols obtained by copolymerizing acrylic monomers using light energy such as ultraviolet rays, electron beams, or the like.

-Silicone polyol-
Specific examples of silicone polyols include vinyl group-containing silicone compounds obtained by polymerizing γ-(meth)acryloxypropyltrimethoxysilane, etc., and α,ω-dihydroxypolydimethylsiloxanes having at least one terminal hydroxyl group in the molecule. , α,ω-dihydroxypolydiphenylsiloxanes.

- Castor oil-based polyol -
Specific examples of castor oil-based polyols include linear or branched polyester polyols obtained by reacting hydrogenated castor oil fatty acids with polyols. Dehydrated castor oil and partially dehydrated castor oil can also be used.

- Fluorinated polyol -
A specific example of the fluorine-based polyol is a linear or branched polyol obtained by a copolymerization reaction of a fluorine-containing monomer and a monomer having a hydroxyl group as essential components. Here, the fluorine-containing monomer includes fluoroolefins such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, and trifluoromethyltrifluoroethylene. be done. Examples of monomers having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and vinyl hydroxyalkyl crotonates. Monomers having hydroxyl groups such as hydroxyl group-containing vinyl carboxylates or allyl esters can be mentioned.

- Olefin polyol -
Specific examples of olefin polyols include diene compounds such as butadiene, isoprene, butene and isobutene, which are polymerized in the presence of anionic polymerization catalysts such as metallic lithium, metallic potassium and metallic sodium, followed by polymerization of ethylene oxide, propylene oxide and the like. Examples thereof include hydrogenated polyols obtained by hydrogenating polyols having a number average molecular weight of 1,000 to 8,000 obtained by addition polymerization of alkylene oxides. Specific examples include hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, hydrogenated polybutene polyol, and hydrogenated polyisobutylene polyol.

- Polythiol compound -
Specific examples of polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6- Hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2 -dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo[2,2,1]pepta-exo-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-thiomalate) -mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3- mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis ( mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercapto acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane), 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl) ) benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2 - bis (mercapto methyleneoxy) benzene, 1,3-bis (mercapto methyleneoxy) benzene, 1,4-bis (meth) mercaptoethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 1,2,3-tri Mercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1 , 3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene , 1,2,3-tris(mercaptomethyleneoxy)benzene, 1,2,4-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,2,3-tris (mercaptoethyleneoxy)benzene, 1,2,4-tris(mercaptoethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2 , 3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene , 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2, 4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,4,5- Tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene, 1,2,4,5-tetrakis( mercaptoethyleneoxy)benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1,4 - naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di(p- methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 2,5- Dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4,6 -tetrachloro-1,5-bis(mercaptomethyl)benzene, 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4, 6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine , 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, 1,2 -bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene 1,3-bis(mercaptoethylthio) ) benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercapto methylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1,2, 3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1,2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3,4-tetrakis (mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene 1,2,4,5-tetrakis(mercaptoethylthio)benzene, bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2- mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl)ethane , 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio ) propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthio methyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-bis(mercaptomethyl)-1 , 4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, hydroxymethylsulfide bis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate), Hydroxyethyl sulfide bis (2-mercaptoacetate), Hydroxyethyl sulfide bis (3-mercaptopropionate), Hydroxypropyl sulfide bis (2-mercaptopropionate), Hydroxypropyl sulfide bis (3-mercaptopropionate), Hydroxymethyl Disulfide bis (2-mercaptoacetate), Hydroxymethyl disulfide bis (3-mercaptopropionate), Hydroxyethyl disulfide bis (2-mercaptopropionate), Hydroxyethyl disulfide bis (3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diolbis(2-mercaptoacetate), 1,4-dithiane-2,5-diolbis(3-mercaptopropionate), thioglycolic acid bis(2-mercaptoethyl ester), bis(2-mercaptoethyl ester) thiodipropionate, bis(2-mercaptoethyl ester) 4,4-thiodibutyrate, bis(2-mercaptoethyl ester) dithiodiglycolate, Bis dithiodipropionate (2-mercaptoethyl ester), bis 4,4-dithiodibutyrate (2-mercaptoethyl ester), bis thiodiglycolate (2,3-dimercaptopropyl ester), bis thiodipropionate (2,3-dimercaptopropyl ester), dithioglycolic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 3,4-thiophenedithiol, 2, 5-dimercapto-1,3,4-thiadiazole and the like can be mentioned.

-Low molecular weight polyol-
Low-molecular-weight polyols are polyols having a number average molecular weight of 500 or less, and specific examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butane. Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3, 3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis( β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

[Isocyanate compound]
Next, the isocyanate compound will be explained. Isocyanate compounds used in urethane (meth)acrylate resins include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, sulfur atom-containing diisocyanates, polyisothiocyanate compounds, and these allophanate-modified polyisocyanates. , isocyanurate-modified polyisocyanate, uretdione-modified polyisocyanate, urethane-modified polyisocyanate, burette-modified polyisocyanate, uretimine-modified polyisocyanate, acyl urea-modified polyisocyanate, etc. may be used alone or in combination of two or more.

- Aromatic Diisocyanate -
Specific examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 4,4′-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl- 4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate , p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, and the like.

-Aroliphatic Diisocyanate-
Specific examples of araliphatic diisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof , ω,ω′-diisocyanato-1,4-diethylbenzene and the like.

- Aliphatic Diisocyanate -
Specific examples of aliphatic diisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene Diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4- diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5, 7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatomethyl esters, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, and the like.

- Alicyclic Diisocyanate -
Specific examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4- isocyanate-n-butylidene) pentaerythritol, hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl- 3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2, 1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5 -(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2, 1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-2-(3- isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane hydrogenated diphenylmethane diisocyanate, Norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate and the like can be mentioned.

-Sulfur atom-containing diisocyanate-
Specific examples of sulfur atom-containing diisocyanates include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, diphenylsulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis(4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3, 3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3 '-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4'- Dimethoxydiphenyldisulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'- diisocyanate, 4-methyldiphenylsulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4 '-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxyphenylethylenesulfone-3,3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester , 4-methyl-3-isocyanatophenylsulfonylanilide-3′-methyl-4′-isocyanate diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3 '-isocyanate, thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate, and the like.

- Polyisothiocyanate compound -
Specific examples of polyisothiocyanate compounds include 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, P-phenylenedi isopropylidene diisothiocyanate, cyclohexane diisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5 -diisothiocyanate-m-xylene, 4,4-diisothiocyanate-1,1'-biphenyl, 1,1'-methylenebis(4-isothiocyanatobenzene), 1,1'-methylenebis(4-isothiocyanate- 2-methylbenzene), 1,1′-methylenebis(4-isothiocyanato-3-methylbenzene), 1,1′-(1,2-ethanediyl)bis(4-isothiocyanatobenzene), 4,4′- diisothiocyanate benzophenone, 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4' -diisocyanate, 2,4,6-triisothiocyanate-3,5-triazine, hexanedioyl diisothiocyanate, nonanedioil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenecarbonyldiisothiocyanate, 1,4 -benzenecarbonyldiisothiocyanate, (2,2'-bipyridine)-4,4'-dicarbonyldiisothiocyanate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), dithiobis(2-iso thiocyanatoethane), 1-isothiocyanato-4-[(2-isocyanate)sulfonyl]benzene, thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene), sulfinylbis(4-isothiocyanatobenzene), dithiobis(4-isothiocyanatobenzene), 4-isothiocyanato-1-[(4-isocyanatophenyl)sulfonyl]-2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isocyanatophenyl ester, 4-methyl-3-isothi Ocyanatobenzenesulfonylanilide-3′-methyl-4′-isocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, 1-isocyanate-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3 -isothiocyanate-1-isothiocyanatobenzene, 2-isothiocyanate-4,6-diisothiocyanate-1,3,5-triazine, 4-isothiocyanate-4'-isothiocyanatodiphenyl sulfide, 2-isothiocyanate-2' - isothiocyanate diethyl disulfide and the like.

(3) Urethane Modified Resin Examples of the urethane modified resin that can be used as the non-radical reactive water-based emulsion (A) include urethane (meth)acrylate resins, and the above compounds having at least one or more active hydrogen groups. and an isocyanate compound and a radically polymerizable unsaturated group-containing oligomer obtained by reacting a hydroxy group-containing acrylate compound with an initiator that causes the polymerization to proceed in the same manner as the radical generator in the present embodiment, Examples include resins polymerized by energy such as ultraviolet rays, electron beams, and heat. The method for producing the urethane (meth)acrylate resin is not particularly limited, but a method of reacting an active hydrogen group-containing compound with an isocyanate compound to prepare an isocyanate-terminated prepolymer and then reacting the hydroxy group-containing acrylate compound, A method of reacting a hydroxy group-containing acrylate compound with an isocyanate compound and then reacting with an active hydrogen group-containing compound can be mentioned.

(4) Polyester resin Specific examples of the polyester resin that can be used as the non-radical-reactive aqueous emulsion (A) include (i) dimerization of the unsaturated fatty acid having 18 carbon atoms used in the production of the polyester polyol described above. A carboxyl group-terminated polyester obtained from a polycondensation reaction of one or more of dicarboxylic acids having 36 carbon atoms or anhydrides thereof and one or more of low-molecular-weight polyols having a molecular weight of 500 or less, polyester (meth)acrylate resin obtained by reacting an epoxy compound containing a β-unsaturated carboxylic acid ester group; Examples include polyester polyols obtained from a polycondensation reaction of one or more dicarboxylic acids or anhydrides thereof and one or more low-molecular-weight polyols having a molecular weight of 500 or less.

(5) Vinyl ester resin A specific example of the vinyl ester resin that can be used as the non-radical-reactive aqueous emulsion (A) is an epoxy (meth)acrylate resin in which an epoxy compound and an unsaturated monobasic acid (if necessary A conventionally known one obtained by an esterification reaction of a saturated dibasic acid) can be used. Such known vinyl ester resins are described, for example, in "Polyester Resin Handbook", Nikkan Kogyo Shimbun, 1988, and "Paint Glossary", edited by Shikizai Kyokai, 1993.

(6) Phenolic resin A specific example of the phenolic resin that can be used as the non-radical-reactive aqueous emulsion (A) is a polycondensation product of phenol or a derivative thereof and an aldehyde compound. It is carried out in the presence of a catalyst such as an acid or base. Phenolic resins obtained when an acid catalyst is used are novolac-type phenolic resins, and specific examples thereof include phenol/formaldehyde novolac resins, cresol/formaldehyde novolac resins, xylylenol/formaldehyde novolac resins, resorcinol/formaldehyde novolak resins and phenol- naphthol/formaldehyde novolak resins and the like.

-Phenol Derivatives-
Phenol derivatives used to obtain phenolic resins include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol and other alkylphenols, methoxyphenol, 2-methoxy-4-methylphenol and other alkoxyphenols, vinylphenol, allylphenol and other alkenylphenols, benzylphenol and other aralkylphenols, methoxycarbonylphenol and other alkoxyphenols arylcarbonylphenols such as carbonylphenol and benzoyloxyphenol; halogenated phenols such as chlorophenol; polyhydroxybenzenes such as catechol, resorcinol and pyrogallol; bisphenols such as bisphenol A and bisphenol F; hydroxyalkylphenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; hydroxyalkylcresols such as hydroxyethylcresol; monoethylene oxide adducts of bisphenol; bisphenol alcoholic hydroxyl group-containing phenol derivatives such as monopropylene oxide adducts of; Carboxyl group-containing phenol derivatives such as hydroxyphenoxybenzoic acid and diphenol are included. Moreover, a methylol compound of the above phenol derivative such as bishydroxymethyl-p-cresol can also be used as the phenol derivative.

-Aldehyde compound-
Aldehyde compounds used to obtain phenolic resins include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, glyceraldehyde, glyoxylic acid. , methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate, and the like. Also, precursors of formaldehyde such as paraformaldehyde and trioxane, ketones such as acetone, pyruvic acid, repulinic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3′-4,4′-benzophenonetetracarboxylic acid can also be used for the reaction. These can be used alone or in combination of two or more.

(7) Epoxy resin Specific examples of epoxy resins that can be used as the non-radical-reactive aqueous emulsion (A) include polyglycidyl ethers of polyhydric phenols having one or more aromatic rings, or alkylene oxide adducts thereof. Glycidyl ether of bisphenol A, bisphenol F, or compounds obtained by adding alkylene oxide to these, aromatic epoxy resins such as epoxy novolak resins, polyglycidyl ethers of polyhydric alcohols having one or more alicyclic rings, or cyclohexene and hydrogenated bisphenol A diglycidyl ether obtained by epoxidizing a compound containing a cyclopentene ring with an oxidizing agent, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl Cyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexyl methyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl- 5,5-spiro-3,4-epoxy)cyclohexane-methodioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane ), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propanedicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxy cycloaliphatic epoxies such as dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and 1,2-epoxy-2-epoxyethylcyclohexane Resins, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol , hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, glycidyl ether of polyhydric alcohol such as diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane and glycerin. Polyglycidyl ethers of polyether polyols obtained by adding two or more kinds of alkylene oxides, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers and phenols of aliphatic higher alcohols, phenol, cresol, butylphenol, In addition, monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, epoxidized soybean oil, epoxidized polybutadiene and other aliphatic epoxy resins.

(8) Melamine resin Examples of the melamine resin that can be used as the non-radical-reactive aqueous emulsion (A) include resins produced by polycondensation of melamine and formaldehyde. Specific examples include methylol melamine and etherification. methylol melamine, benzoguanamine, methylol benzoguanamine, etherified methylol benzoguanamine, condensates thereof, and the like.

(9) Olefin-based resin Specific examples of the olefin-based resin that can be used as the non-radical-reactive aqueous emulsion (A) include hydrogenated styrene-isoprene copolymers and hydrogenated styrene-butadiene copolymers. , polyisobutylene, hydrogenated polybutene, hydrogenated polybutadiene, hydrogenated polyisoprene, polystyrene, and the like.

(10) Silicone resin Examples of silicone resins that can be used as the non-radical-reactive aqueous emulsion (A) include silicone resins having dimethylpolysiloxane as a basic skeleton. Silicone resins include addition reaction type, condensation reaction type, ultraviolet curing type, electron beam curing type, and the like. Among them, the addition reaction type silicone resin is highly reactive and excellent in productivity, and compared with the condensation reaction type, it has advantages such as small change in release force after production and no curing shrinkage, and is preferably used. A specific example of the addition reaction type silicone resin is an organopoly having two or more alkenyl groups having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a propenyl group, and a hexenyl group at the ends and/or side chains of the molecule. Siloxane is mentioned. When using such an addition reaction type silicone resin, it is preferable to use a cross-linking agent and a catalyst together. Examples of the cross-linking agent include an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, specifically a dimethylhydrogensiloxy end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer. Coalescing, trimethylsiloxy group end-blocked dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group end-blocked methylhydrogenpolysiloxane, poly(hydrogensilsesquioxane) and the like. Catalysts used include fine particle platinum, fine particle platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, and platinum group metal compounds such as palladium and rhodium. etc. By using such a catalyst, the curing reaction can proceed more efficiently.

(emulsifier)
The emulsifier is not particularly limited as long as it is capable of forcibly emulsifying or emulsion-polymerizing the above-mentioned resin into an aqueous emulsion, and can be appropriately selected from known emulsifiers and used. Examples of the emulsifier include, but are not particularly limited to, anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers and the like, which are generally used for emulsions, in order to ensure emulsion stability. In addition, as described above, the non-radical reactive aqueous emulsion (A) can be obtained by forced emulsification or emulsion polymerization using the above resin and emulsifier. The method is also not particularly limited, and a known method can be appropriately selected according to the types of resin and emulsifier.

Examples of anionic emulsifiers include ether carboxylic acids such as sodium lauryl ether acetate or salts thereof, sulfuric acid esters such as sodium lauryl sulfate or salts thereof, sodium (poly)oxyethylene lauryl sulfate, triethanolamine (poly)oxyethylene laurate, Examples include, but are not limited to, sulfonates such as sodium dodecylbenzenesulfonate, phosphate esters such as sodium lauryl phosphate or salts thereof, and fatty acid salts such as sodium laurate.
Nonionic surfactants include, for example, fatty alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, polyhydric alcohol fatty acid esters such as sorbitan monolaurate, fatty acid alkanolamides such as coconut oil fatty acid diethanolamide, (poly ) oxyalkylenealkylphenyl ethers, (poly)oxyalkylenealkylamines, and dialkylamine oxides such as lauryldimethylamine oxide.
Cationic emulsifiers include primary to tertiary amine salts, pyridinium salts, alkylpyridinium salts and the like.

The content of the non-radical-reactive aqueous emulsion (A) in the coating composition is not particularly limited, but from the viewpoint of film-forming properties, adhesion properties, and wet skin prevention properties, the total solid content of the coating composition is preferably 10 to 70% by mass, more preferably 30 to 50% by mass in terms of solid content.

<Colloidal silica (B)>
Colloidal silica (B) densifies the microscopic voids in the concrete, thereby imparting waterproofness to the concrete and further preventing the concrete surface from becoming wet. In addition, colloidal silica (B) can suppress permeation of oxygen, carbon dioxide, and chloride ions, which are factors that deteriorate concrete, and can contribute to extending the life of concrete. Furthermore, the use of colloidal silica (B) makes it possible to make the coating film colorless and transparent after fading of the radical-reactive dye (D), thereby exhibiting excellent undercoat visibility.

Here, the colloidal silica (B) used in the coating composition is not particularly limited, but has an average primary particle size of 10 to 500 nm and is dispersed in water or in an organic solvent. More preferably, a type in which substantially spherical silica particles having an average particle size of 5 to 100 nm are dispersed in a medium, silica aggregated into chains having a thickness of 5 to 50 nm and a length of about 40 to 400 nm. A type in which particles are dispersed in a medium, a pearl necklace-shaped type in which spherical silica particles with an average particle size of 10 to 50 nm are linked in a pearl necklace shape with a length of 50 to 400 nm dispersed in a medium, an average particle size of 5 to 50 nm and a cyclic type in which silica sol is cyclically aggregated and dispersed in a medium. In the present embodiment, it is preferable to use colloidal silica having an average particle size of 10 to 100 nm from the viewpoint of imparting waterproofness by densifying the microscopic voids of the concrete and preventing the concrete from becoming wet. Particle size can be measured by a laser diffraction scattering method.

The method for producing the silica sol used as colloidal silica (B) is not particularly limited, and known techniques can be used. a method of condensing active silicic acid obtained by a method of neutralizing an alkali silicate with a mineral acid; or a method of obtaining an organic solvent-based silica sol (organo silica sol) by replacing the water in the aqueous silica sol with an organic solvent by a distillation method or the like. As the silica sol used for the colloidal silica (B), either an aqueous silica sol or an organic solvent-based silica sol can be used as appropriate. A silica sol is preferred, and an alkaline type silica sol having a pH of 8 to 10 containing Na contained during production of the aqueous silica sol is more preferred.

Specific examples of colloidal silica of a type in which substantially spherical or spherical silica particles are dispersed in water include, for example, Snowtex-20, Snowtex-O, Snowtex-C and Snowtex manufactured by Nissan Chemical Industries, Ltd. Tex-S, Snowtex-50, Snowtex-XL, and Adelite AT-20, AT-20N, AT-20A and AT-300 manufactured by Asahi Denka Kogyo Co., Ltd., and the like.

Specific examples of chain type colloidal silica in which silica particles aggregated in a chain form are dispersed in water include SNOWTEX-UP and SNOWTEX-OUP manufactured by Nissan Chemical Industries, Ltd., for example.

Specific examples of pearl necklace type colloidal silica in which spherical silica particles linked in a pearl necklace shape are dispersed in a medium include SNOWTEX-PS-S and SNOWTEX-PS-M manufactured by Nissan Chemical Industries, Ltd. , Snowtex-PS-SO and Snowtex-PS-MO, MP-2040, MP-4540M and the like.

The content of colloidal silica (B) in the coating composition is not particularly limited. ~90% by mass is preferable, and 50 to 70% by mass is more preferable.

<Radical generator (C)>

Next, the radical generator (C) for fading the dye (D) by a radical reaction will be described. The radical generator (C) is not particularly limited as long as it generates radical species that contribute to the fading reaction of the radical-reactive dye (D). A photo-radical generator that generates radical species upon exposure to radiation such as a photo-radical generator can be used.

The content of the radical generator (C) in the coating composition is not particularly limited, but from the viewpoint of fading effect, it is preferably 0.001 to 1% by mass based on the total solid content of the coating composition. , more preferably 0.01 to 0.5% by mass, and particularly preferably 0.03 to 0.3% by mass.

(1) Thermal radical generator Specific examples of the thermal radical generator are not particularly limited, but peroxydicarbonates such as di-2-ethylhexylperoxydicarbonate, t-butylperoxybenzoate, t-butylperoxy-2- Peroxy esters such as ethylhexanoate, t-butylperoxyisopropyl carbonate, t-hexylperoxyisopropyl carbonate, di(t-butylperoxy)-2-methylcyclohexane, di(t-butylperoxy)3,3,5- and peroxyketals such as trimethylcyclohexane and di(t-butylperoxy)cyclohexane. As the thermal radical generator, a thermal radical generator that can be used in polymerization in an aqueous solution can be used. Specific examples of thermal radical generators mainly used in polymerization in an aqueous solution include sodium persulfate, potassium persulfate, Persulfates such as ammonium persulfate, organic peroxides such as t-butyl hydroperoxide and cumene hydroperoxide, redox compounds such as hydrogen peroxide and tartaric acid, trade name "V-50" (Wako Pure Chemical Industries ( Co., Ltd.) and other water-soluble azo initiators. Thermal radical generators can be used alone or in combination of two or more. When a thermal radical generator is used as the radical generator (C), it can be added in an amount of 0.1 to 200% by mass based on the total amount of the radical-reactive dye (D) in order to obtain an excellent discoloration effect. Preferably, it is more preferably added in an amount of 50 to 100% by mass.

(2) Photo-radical generators Specific examples of photo-radical generators are not particularly limited, but are benzoin ether-based photo-radical generators, acetophenone-based photo-radical generators, α-ketol-based photo-radical generators, and aromatic sulfonyl chlorides. photoradical generators, photoactive oxime photoradical generators, benzoin photoradical generators, benzyl photoradical generators, benzophenone photoradical generators, ketal photoradical generators, thioxanthone photoradical generators, An acylphosphine oxide photoradical generator or the like can be used. These photo-radical generators can be used alone or in combination of two or more. When a photo-radical generator is used as the radical generator (C), it can be added in an amount of 0.1 to 150% by mass based on the total amount of the radical-reactive dye (D) in order to obtain an excellent discoloration effect. Preferably, it is more preferably added in an amount of 1 to 100% by mass.

- Benzoin ether photoradical generator -
Specific examples of benzoin ether photoradical generators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one ( (trade name: Irgacure 651, manufactured by BASF), anisole methyl ether, and the like.

- Acetophenone Photoradical Generator -
Specific examples of acetophenone photoradical generators include 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (trade name: Irgacure 1173, manufactured by BASF), methoxyacetophenone, and the like.

-α-Ketol Photoradical Generator-
Specific examples of α-ketol photoradical generators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1. -on and the like.

- Aromatic sulfonyl chloride photoradical generator -
Specific examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride.

-Photoactive oxime photoradical generator-
Specific examples of photoactive oxime photoradical generators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

- Benzoin-based photoradical generator -
Specific examples of benzoin-based photoradical generators include benzoin.

- Benzyl-based photoradical generator -
Specific examples of benzyl-based photoradical generators include benzyl and the like.

- Benzophenone Photoradical Generator -
Specific examples of benzophenone photoradical generators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, and 4-(methylphenylthio). Phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis (dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, and the like.

-Ketal Photoradical Generator-
Specific examples of ketal-based photoradical generators include benzyl dimethyl ketal.

-Thioxanthone Photoradical Generator-
Specific examples of thioxanthone photoradical generators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and isopropylthioxanthone. , 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

-Acylphosphine Photoradical Generator-
Specific examples of acylphosphine photoradical generators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1 -methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octyl Phosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-di ethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)( 2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4- dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2- Phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, Bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) )-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4 ,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1 , 10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide and the like.

(3) Others - Photosensitizer -
Moreover, in order to enhance the photoreactivity, the photoradical generator and the photosensitizer may be used in combination. The photosensitizer is not particularly limited and known ones can be used. Specific examples include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- isoamyl dimethylaminobenzoate, 4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone and the like.

- radical reaction inhibitor -
In addition, a radical scavenger can be used together in order to adjust the reaction rate of the radical reaction between the radical generator (C) and the dye (D). Specific examples of radical scavengers include 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, 2,6-di-tert-butyl-p-cresol, 1,1-diphenyl-2- Picrylhydrazyl free radical, hydroquinone, hydroquinone monomethyl ether, phenothiazine, ammonium-N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine aluminum salt, and the like. These radical scavengers can be used alone or in combination of two or more, and are preferably added at 100 ppm to 5,000 ppm with respect to the radical generator (C).

<Radical Reactive Dye (D)>
The radical-reactive dye (D) used in the coating composition of the present embodiment can be used without particular limitation as long as it is a dye that fades due to a radical reaction. For example, when the coating composition of the present embodiment is used as a coating agent for covering a concrete structure, since the coating composition is colored with the radical reactive dye (D) at the time of application, it is necessary to visually confirm the coating state of the concrete surface. can be done. Therefore, the presence or absence of coating unevenness due to construction can be easily confirmed, and the influence of coating unevenness can be reduced. Further, after the radical-reactive dye (D) fades, the original color of the coating composition can be obtained, for example, it can be colorless and transparent.

Techniques for confirming the degree of coloring of the coating composition include a direct visual observation technique and a technique using a measuring instrument such as a visible/ultraviolet spectrophotometer. In particular, a wavelength in the visible light region of 400 nm to 800 nm can be used to determine the presence or absence of fading. Here, the index of fading is not particularly limited, but in measurement with a visible/ultraviolet spectrophotometer, the absorbance at the wavelength showing the maximum value in the range of 400 to 800 nm before heat and/or light irradiation is , preferably 0.5 abs or less, more preferably 0.3 abs or less, and particularly preferably 0.1 abs or less after irradiation with heat and/or light. When the absorbance is 0.5 abs or less, coloration is not visually recognized, and the base visibility can be enhanced. In addition, although the mechanism of fading is not clear at this time, the conjugated system of the dye changes due to the reaction with the radical species, and in particular the opposite color (when the visual is red, the wavelength of blue decreases). presumed to fade. The maximum value in the range of 400 to 800 nm before heat and/or light irradiation is not particularly limited, but from the viewpoint of visibility, it is preferably 0.6 to 1.5 abs. 7 to 1 abs is more preferred.

The content of the radical-reactive dye (D) is not particularly limited as long as it does not affect the performance. It is preferably adjusted in the range of 0.0001% to 5% by mass, more preferably 0.03% to 4% by mass.

The radical-reactive dye (D) is not particularly limited. and phenothiazine derivatives having These dyes fade by reacting with radical species generated from the radical generator (C) decomposed by heat and/or light irradiation.

(1) Dye having a tetraterpene structure Examples of the radical-reactive dye (D) having a tetraterpene structure include cartenoid dyes and xanthophyll dyes. These dyes can be faded by radical species generated from the radical generator (C) by irradiation with activation energy such as heat or light irradiation.

[Cartenoid pigment]
Specific examples of cartenoid pigments include α-carotene, β-carotene, γ-carotene, ε-carotene, δ-carotene, and lycopene, which can be used alone or in combination of two or more. For example, lycopene is a compound having the structure:

[Xanthophyll-based dye]
Specific examples of xanthophyll pigments include lutein, zeaxanthin, canthaxanthin, fucoxanthin, astaxanthin, antheraxanthin, violaxanthin, diazinoxanthin, diatoxanthin, β-cryptoxanthin, capsanthin, myxoxanthophyll, citranaxanthin, Dinoxanthin, flavoxanthin, neoxanthin, rhodoxanthin, and rubixanthin can be used alone or in combination of two or more.

(2) Phenothiazine Derivative The 3,7-diamino-10H-phenothiazine structure of the phenothiazine derivative that can be used as the radical-reactive dye (D) can be represented by the following general formula (1).

（式中、Ｒ¹～Ｒ⁶は、各々独立して、水素、ハロゲンを有していてもよい炭素数１～４のアルキル基、及び、炭素数２～４のアルケニル基を示す。式中、ＨＸは、Ｘが、Ｃｌ、Ｂｒ、Ｉ、Ｆから選択されるモノプロトン酸を示す。）

(In the formula, R ¹ to R ⁶ each independently represent hydrogen, an optionally halogenated alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. , HX denotes a monoprotonic acid in which X is selected from Cl, Br, I, F.)

R ¹ to R ⁶ in the formula (1) represent any one of hydrogen, an optionally halogenated alkyl group having 1 to 4 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms. R ¹ to R ⁶ may be the same or different. Examples of alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group and tert-butyl group. Examples of the alkenyl group having 2 to 4 carbon atoms include linear alkenyl groups such as vinyl group and allyl group. Alternatively, the halogen-containing alkyl group having 1 to 4 carbon atoms includes -CF ₃ , -CH ₂ CF ₃ , -CF ₂ CF ₃ and the like.
In formula (1), HX is a monoprotonic acid in which X is selected from Cl, Br, I and F.

The 3,7-diamino-10H-phenothiazine structure represented by formula (1) has the following structure in which R ⁵ and R ⁶ are hydrogen, R ¹ to R ⁴ are methyl groups, and HX is chlorine monoprotonic acid. The 3,7-bis(dimethylamino)phenothiazinium chloride shown is particularly preferred.

When 3,7-bis(dimethylamino)phenothiazinium chloride is irradiated with active energy such as heat or light irradiation, the radical species generated from the radical generator interlocks with the curing state, and the fading effect is particularly noticeable. high.

In addition to phenothiazine derivatives having a 3,7-diamino-10H-phenothiazine structure, phenothiazine, 1-methylphenothiazine, 2-methylphenothiazine, 3-methylphenothiazine, 4-methylphenothiazine, 1-ethyl, as long as the performance does not decrease Phenothiazine, 2-ethylphenothiazine, 3-ethylphenothiazine, 4-ethylphenothiazine, 1-methoxyphenothiazine, 2-methoxyphenothiazine, 3-methoxyphenothiazine, 4-methoxyphenothiazine, 1-ethoxyphenothiazine, 2-ethoxyphenothiazine, 3-ethoxy Phenothiazine, 1-chlorophenothiazine, 2-chlorophenothiazine, 3-chlorophenothiazine, 4-chlorophenothiazine, 1-bromophenothiazine, 2-bromophenothiazine, 3-bromophenothiazine, 4-bromophenothiazine, 1,2-dimethylbromophenothiazine, 1,3-dimethylphenothiazine, 1,4-dimethylphenothiazine, 1,6-dimethylphenothiazine, 1,7-dimethylphenothiazine, 1,8-dimethylphenothiazine, 1,9-dimethylphenothiazine, 2,3-dimethylphenothiazine, 2 , 4-dimethylphenothiazine, 2,6-dimethylphenothiazine, 2,7-dimethylphenothiazine, 2,8-dimethylphenothiazine, 3,6-dimethylphenothiazine, 3,7-dimethylphenothiazine, 1,2-dimethoxyphenothiazine, 1, 4-dimethoxyphenothiazine, 2,3-dimethoxyphenothiazine, 2,7-dimethoxyphenothiazine, 2,8-dimethoxyphenothiazine, 3,7-dimethoxyphenothiazine, 1,2-dichlorophenothiazine, 1,3-dichlorophenothiazine, 1,4 -dichlorophenothiazine, 1,7-dichlorophenothiazine, 1,8-dichlorophenothiazine, 2,3-dichlorophenothiazine, 2,4-dichlorophenothiazine, 2,6-dichlorophenothiazine, 2,7-dichlorophenothiazine, 2,8- Dichlorophenothiazine, 3,7-dichlorophenothiazine, 1,3-dibromophenothiazine, 2,4-dibromophenothiazine, 2,7-dibromophenothiazine and 3,7-dibromophenothiazine can be used in combination.

《Coating agent for covering concrete structures》
The coating composition of the present embodiment can be suitably used as a coating agent for covering concrete structures. In addition to the coating composition described above, the coating agent for coating concrete structures may contain known additives such as thickeners and film-forming aids depending on the purpose.

(Film-forming aid)
As the film-forming aid, various commercially available film-forming aids can be used, and the film-forming properties can be enhanced by using the film-forming aid together. Specific examples of film-forming aids include dipropylene glycol-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, ethylene glycol mono-2-ethylhexyl ether, diethyl adipate, 2 , 2,4-trimethylpentane-1,3-diol monoisobutyrate and other polyhydric alcohol alkyl ethers, organic acid esters, and organic solvents having a boiling point of over 100°C.
The addition amount of the film-forming aid is not particularly limited, but from the viewpoint of achieving both the storage stability of the film-forming coating composition at room temperature, it should be 0.00% relative to the total solid content of the coating composition. 001 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.1 to 1% by mass.

<<Coating Method for Concrete Structure Coating Agent>>
A coating method for a coating agent for covering concrete structures (hereinafter sometimes simply referred to as a "coating method") comprises a step of applying a coating agent for covering concrete structures to a concrete base material to form a coating film; a step of irradiating at least part of the concrete structure coating agent applied to the concrete base material with heat and/or light to make the concrete structure coating agent colorless and transparent. The coating method of the present embodiment may include any process such as a drying process as long as the effects of the present invention are not affected.

The coating method of the present embodiment includes a step of applying a concrete structure coating agent to a concrete base material to form a coating film. As the concrete base material, any base material formed using concrete having a pore size of 500 nm or less can be used without any particular problem. Also, the method of applying the coating agent for covering concrete structures is not particularly limited, and known applying means such as coating, spraying, and immersion can be appropriately employed depending on the viscosity of the coating agent. For example, when the viscosity of the coating agent is low, it may be applied in multiple layers or thickened with a thickener.

The film thickness of the coating film is not particularly limited. , preferably 0.2 mm to 1.5 mm, more preferably 0.4 mm to 1 mm.

Next, in the coating method of the present embodiment, at least a portion of the concrete structure coating agent applied to the concrete base material is irradiated with heat and/or light to make the concrete structure coating agent colorless and transparent. and According to the coating method of the present embodiment, the radical reactive dye (D) is faded by irradiating heat and/or light to the concrete structure coating coating agent (coating film) applied to the concrete base material. The coating film formed by the coating agent for coating concrete structures can be made colorless and transparent. In the coating process of this embodiment, it is preferable that the “colorless and transparent” can be completely colorless and transparent to the extent that it can be visually confirmed, but it is sufficient if the concrete surface can be visually observed through the coating film. It is not necessary for the film to become colorless and transparent. Regarding the criteria for making the coating film colorless and transparent, for example, as described above, the absorbance at the wavelength showing the maximum value of the coating film in the range of 400 to 800 nm before heat and/or light irradiation can be used as a standard. The absorbance is preferably 0.5abs or less after heat and/or light irradiation.

The conditions for applying heat and/or light to the coating agent for coating concrete structures are not particularly limited, and are appropriately set according to the types and amounts of the radical-reactive dye (D) and radical generator (C) used. be able to. For example, when the radical-reactive dye (D) is faded using a thermal radical generator, the temperature is set to 60 to 100°C (preferably 60 to 80°C) from the viewpoint of the appearance of the coating film and prevention of deterioration of the concrete. , the heating time can be 0.01 to 1 hour (preferably 0.1 to 0.5 hour). Further, when the radical-reactive dye (D) is faded using a photo-radical generator, ultraviolet rays, electron beams, radiation, etc. can be used. ² (preferably 1 to 100 mW/cm ² ), and the irradiation energy can be 100 to 10000 mJ/cm ² (preferably 500 to 3000 mJ/cm ² ). Moreover, the coating agent for covering a concrete structure of the present embodiment may be configured such that the coating film of the coating agent for covering a concrete structure is simultaneously cured by the irradiation of the heat or light.
Further, the heat and/or light irradiation conditions described above may be set so that the color fades over time due to sunlight (ultraviolet rays), for example.

(adhesion strength)
In addition, the adhesion strength between the coating film formed by the concrete structure coating coating agent of the present embodiment and the concrete plane conforms to the Japan Society of Civil Engineers standard JSCE K-531-2013) "Tensile test method for continuous fiber reinforcement". In the adhesion test, the adhesion strength between the concrete base material and the coating film is preferably 1 N/mm ² or more, more preferably 1.5 N/mm ² or more, and 2 N/mm ² or more. Especially preferred. The upper limit of the adhesion strength is not particularly limited, but can be, for example, 1.5 to 7 N/mm ² or 2 to 5 N/mm ² . The "adhesion strength" specifically means the value at the maximum load when tensile force is applied vertically to the test surface. Also, the adhesion strength can be measured by the method described in Examples below.

(Chloride ion permeability)
The chloride ion permeability of the coating film formed by the concrete structure coating coating agent of the present embodiment is a chloride ion permeability test in accordance with NEXCO Standard Test Method 425-2004 "Durability test method for preventing flaking". In the above, using the chloride ion concentration measured by the chloride ion analysis method of JIS K0101, the chloride ion permeability of the coating film calculated from the following formula (1) is 0.005 g/m ² day or less. is preferably 0.001 g/m ² ·day or less. Further, the lower limit of the chloride ion permeability is not particularly limited, and the lower the better. The "chloride ion permeability" can be measured by the method described in Examples below. In the following formula (1), the amount (V) of deionized water in the cell and the chloride ion permeation area (A) are determined by the amount of water and the size of the sample at the time of evaluation.

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ²・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ²）〕

[Cl: chloride ion permeability (g/m ² day), V: amount of deionized water in the cell (ml), M: chloride ion concentration (mg/l), A: chloride ion permeation area (cm ² )]

(neutralization depth)
In a neutralization inhibition test in accordance with the "test method for accelerated neutralization of concrete" specified in JIS A1153:2012, 28 The neutralization depth of the coating film after resting for a day is preferably 1 mm or less, more preferably 0 mm. The "neutralization depth" can be measured by the method described in Examples below.

Although aspects of the present invention have been described above, the present invention is not limited to the above-described embodiments.

<<Preparation of coating composition>>
Colloidal silica (or titanium oxide) and distilled water were mixed and stirred at normal temperature (about 20° C.) according to the table below so that the solid content of each formulation of the coating composition was 30% by mass. After that, the water-based emulsion, the radical generator, and the dye were equally mixed with stirring, and the mixture was stirred until uniform to prepare a coating agent for each composition.

《Evaluation of Concrete Structure Covering Method》
The coating agents prepared in Examples and Comparative Examples were used in formulations, and the following evaluations were carried out.

<Appearance of coating film>
After drying, the appearance of the coating film before heat or light irradiation treatment was visually observed for the presence or absence of floating, cracking, etc. of the coating film, and evaluated according to the following evaluation criteria. In Comparative Example 3, cracking of the coating film was confirmed.
Evaluation A: No lifting or cracking of the coating film was observed.
Evaluation C: Lifting or cracking of the coating film was confirmed.

<Fadeability>
The prepared coating agent was applied to a 50 μm PET film with a spatula in such an amount that the dry film thickness would be as shown in the table below, and dried and cured at 20° C. for 24 hours. The absorbance (unit: abs) of the wavelength showing the maximum value in the range of 400 to 800 nm after heat or light irradiation treatment was measured in the measurement of the obtained coating film with a visible/ultraviolet spectrophotometer. An absorbance of 0.5 abs or less indicates excellent fading resistance.
The irradiation conditions when using a thermal radical generator are a heat treatment at 100° C. for 10 minutes, and the irradiation conditions when a photoradical generator is used are an irradiation intensity of 80 mW/cm ² at 365 nm and an irradiation energy of 1. ,000 mJ/cm ² was irradiated with UV light.

<Underground visibility>
The base visibility of the coating film was evaluated according to the following criteria using the absorbance at the wavelength showing the maximum value in the range of 400 to 800 nm after heat or light irradiation treatment in the above-mentioned fading property evaluation.
(Evaluation criteria)
Evaluation A: The absorbance was 0.5 abs or less, and the base visibility was excellent.
Evaluation C: The absorbance was over 0.5 abs, indicating poor visibility.

<Adhesion>
The surface of a concrete flat plate (300 mm×300 mm) defined in JIS A 5371-2013 was subjected to keren treatment with a disk sander. The prepared coating agent was applied to the concrete surface at 20° C. with a spatula in such an amount that the dry film thickness would be as shown in the table below, and dried and cured for 168 hours. Thereafter, an epoxy resin (manufactured by Konishi Co., Ltd., Quick Mender) was used on the specimen, and a jig was attached to the specimen, and a test was conducted using a construction research type adhesion tester. Specifically, a tensile force was applied vertically to the test surface, and the value at the maximum load was measured.
When the value at the maximum load is 1 N/mm ² or more, it means that the adhesion between the coating film and the concrete surface is excellent.

<Prevention of wet skin>
The surface of a concrete flat plate (300 mm x 300 mm) defined in JIS A 5371 was subjected to shaving with a disk sander. The prepared coating agent was applied to the concrete surface with a spatula at 20 ° C. so that the dry film thickness would be the thickness shown in the table below, and after being subjected to fading treatment, it was dried and cured for 168 hours. After that, 1) after water was sprayed, and 2) after application of a colorless and transparent two-component polyurethane paint, the presence or absence of wet skin was visually confirmed according to the following criteria.
(Evaluation criteria)
Evaluation A: In both cases of 1) and 2), no wet surface was observed on the concrete surface.
Evaluation C: In at least one of 1) and 2), a wet surface was confirmed on the concrete surface.

<Chloride ion permeability>
The surface of a mortar specimen specified in JIS R5201 was sandblasted. The prepared coating agent was applied to the mortar surface with a spatula under conditions of 20° C. in such an amount that the dry film thickness would be the thickness shown in the table below, and dried and cured for 168 hours. The specimen was cut to a size of φ60 mm, and a chloride ion permeability test in accordance with the NEXCO standard test method 425-2004 "Durability test method for preventing flaking" was performed to determine the amount of chlorine ions of sodium chloride (3% solution). Permeabilization was allowed to stand at 40° C. for 30 days. After that, using the chloride ion concentration measured by the chloride ion analysis method of JIS K0101, the chloride ion permeability was calculated from the following formula (1). The amount of deionized water in the cell and the chloride ion permeation area were determined by the amount of water and the size of the sample at the time of evaluation, and were V=200 ml and A=19.63 cm ² , respectively.

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ²・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：測定した塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ²）〕

[Cl: chloride ion permeability (g/m ² day), V: amount of deionized water in the cell (ml), M: measured chloride ion concentration (mg/l), A: chloride ion permeation area ( ^cm2 )]

The obtained chloride ion permeability is most preferably less than 0.002 g/m ² ·day, and if it is 0.002 or more and 0.005 g/m ² ·day or less, there is no particular problem. On the other hand, when the chloride ion permeability exceeds 0.005 g/m ² ·day, it indicates that the effect of inhibiting chloride ion permeability is poor.

<Neutralization prevention>
In accordance with JIS A1153: 2012, the "test method for accelerated neutralization of concrete", a coating agent prepared on the opposite five surfaces of a mortar specimen (100 mm × 100 mm × 100 mm) was applied at 20 ° C. was applied with a spatula so that the dry film thickness would be the thickness shown in the table below. After that, the test specimen cured at 20 ° C. for 168 hours was treated with an epoxy resin (manufactured by Konishi Co., Ltd., "E2500") having performance specified in JIS K5664. It was coated and hardened for 14 days at 20°C. The sample was left in an environmental chamber with a temperature of 30° C., a relative humidity of 60% and a carbon dioxide concentration of 5% for 28 days, and then cured under conditions of a temperature of 20° C. and a relative humidity of 60% for 24 hours. afterwards. A 1% alcohol solution of phenolphthalein is sprayed on the cross section of the test piece split into two pieces, and the depth of the region (distance in the thickness direction from the surface) that does not turn red is neutralized. It was measured.
When the depth of the obtained neutralized region is 0.0 mm, the neutralization resistance is most excellent, and when it is more than 0.0 mm and 1.0 mm or less, the neutralization resistance The results were satisfactory. On the other hand, when the depth of the neutralized region exceeds 1.0 mm, it indicates that the neutralization prevention property is poor.

As shown in each table, the coating agents of Examples showed excellent effects in each evaluation.
On the other hand, Comparative Example 1, which used Formulation 6 containing natural rubber as an aqueous emulsion, exhibited low adhesion. This is because natural rubber generally has an isoprene structure with unsaturated bonds as the main component, and is radically reactive. It is presumed that the adhesion decreased due to the treatment. Comparative Example 1 was also inferior in chloride ion permeability and neutralization resistance.
In Comparative Example 2, Formulation 9 did not contain colloidal silica, and was particularly inferior in wet skin prevention, chloride ion permeability, and neutralization inhibition. In addition, in Comparative Example 3 using Formulation 10 containing no water-based emulsion, cracks occurred in the coating film, and each evaluation could not be performed.
In Comparative Example 4, in which compound 15 containing titanium oxide instead of colloidal silica was used, the concrete surface turned white due to the titanium oxide, and the base visibility and discoloration were poor.
Comparative Examples 5-6 used Formulations 19 and 20 with non-radical reactive dyes, and the dyes did not fade due to radical reactions. For this reason, although it is excellent in wet skin prevention properties, it is inferior in base visibility and color fading resistance.

Claims (10)

at least,
a non-radical reactive aqueous emulsion (A);
colloidal silica (B);
a radical generator (C);
a radical-reactive dye (D);
A coating composition containing 2. The coating composition according to claim 1, wherein said radical-reactive dye (D) comprises a compound containing a tetraterpene structure. 3. The coating composition according to claim 2, wherein the compound containing a tetraterpene structure is at least one selected from cartenoid pigments and xanthophyll pigments. The radical-reactive dye (D) according to any one of claims 1 to 3, comprising a phenothiazine derivative containing a 3,7-diamino-10H-phenothiazine structure represented by the following general formula (1). coating composition.

(In the formula, R ¹ to R ⁶ each independently represent hydrogen, an optionally halogenated alkyl group having 1 to 4 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. In the middle, HX denotes a monoprotonic acid in which X is selected from Cl, Br, I, and F.) The radical-reactive dye (D) exhibits a maximum absorbance at a wavelength in the range of 400 to 800 nm before heat and/or light irradiation, in measurement with a visible/ultraviolet spectrophotometer, after heat and/or light irradiation. The coating composition according to any one of claims 1 to 4, which is 0.5 abs or less. A coating agent for covering a concrete structure, comprising the coating composition according to any one of claims 1 to 5. A step of applying the coating agent for covering a concrete structure according to claim 6 to a concrete base material to form a coating film;
a step of irradiating at least part of the concrete structure coating agent applied to the concrete base material with heat and/or light to make the concrete structure coating agent colorless and transparent;
A coating method for a coating agent for covering concrete structures. In an adhesion test conforming to the Japan Society of Civil Engineers standard JSCE K-531-2013) "Tensile test method for continuous fiber reinforcement", the adhesion strength between the concrete base material and the coating film is 1 N / mm ² or more. The coating method according to claim 7. In a chloride ion permeability test in accordance with NEXCO Standard Test Method 425-2004 "Durability test method for preventing flaking", the chloride ion concentration measured by the chloride ion analysis method of JIS K0101 was used, and the following formula ( The coating method according to claim 7, wherein the chloride ion permeability of the coating film calculated from 1) is 0.005 g/ ^m2 ·day or less.

[Cl: chloride ion permeability (g/m ² ·day), V: amount of deionized water in the cell (ml), M: chloride ion concentration (mg/l), A: chloride ion permeation area (cm ² )] In the test of neutralization resistance in accordance with the "test method for accelerated neutralization of concrete" specified in JIS A1153:2012, 28 8. The coating method according to claim 7, wherein the neutralization depth of said coating film after standing still for days is 1 mm or less.