JP6574600B2 - Water-based resin dispersion for water and sewage lining materials and water and sewage lining materials - Google Patents

Description

  The present invention relates to an aqueous resin dispersion for water and sewage lining materials and a coating for lining materials.

  In sewerage facilities, microorganisms that exist on the surface in contact with concrete sewage produce sulfuric acid from sewage-derived hydrogen sulfide. The generated sulfuric acid corrodes the concrete to which the alkaline material is applied.

  As a countermeasure against this corrosion, an anticorrosion coating method can be employed in which contact between concrete and sulfuric acid is prevented by coating the concrete with an organic resin. In addition to such construction methods, it is conceivable that concrete or cross-section repair mortar itself has sulfuric acid resistance. With such concrete, durability of concrete structures can be improved. In some cases, it is expected that the anticorrosion coating can be omitted. Furthermore, for the purpose of improving the performance of the mortar, a method of mixing an organic polymer (aqueous resin dispersion such as latex, powder dispersion, etc.) into the mortar has been proposed.

  For example, in Patent Document 1, as a method for producing an anticorrosion concrete pipe, a polymerizable monomer in which 85% by mass or more of a (meth) acrylic polymerizable monomer having a water solubility at 25 ° C. of less than 1% and / or vinyl chloride is used. Emulsion polymer obtained by emulsion polymerization of polymer mixture, cement, adhesive layer made of inorganic aggregate, resin layer on the adhesive layer (vinyl chloride, (meth) acrylic polymerization with water solubility of 1 g / water less than 100 g) Formed from an emulsion polymer obtained by emulsion polymerization of a polymerizable monomer mixture containing a polymerizable monomer) or a resin mortar layer (vinyl chloride, 25 ° C. water solubility 1 g / (meth) acrylic less than 100 g water) It has been proposed to provide an emulsion polymer obtained by emulsion polymerization of a polymerizable monomer mixture containing a polymerizable monomer and an aggregate.

  Moreover, in patent document 2, the polymerizable monomer mixture which consists of 80-99 mass% of polymerizable monomers copolymerizable with 1-20 mass% of alkoxysilyl group containing polymeric monomers on the inner surface of a concrete layer is provided. An anticorrosion concrete pipe characterized by comprising an anticorrosion lining layer comprising a copolymer having a glass transition temperature of −35 to 50 ° C. obtained by emulsion copolymerization as a constituent component has been proposed.

JP-A-10-291266 JP-A-9-194272

  The techniques described in Patent Documents 1 and 2 are used only for a new concrete pipe that requires centrifugal lining and steam curing. That is, using the emulsions used in these documents for repairing existing water and sewage systems is difficult in terms of workability, film formability, water resistance, and sulfuric acid resistance, and there is still room for improvement in these characteristics. It can be said that there is.

  The present invention has been made in view of the above-mentioned problems of the prior art, and a water and sewage lining excellent in workability, film formability, water resistance and sulfuric acid resistance when used for repairing an existing water and sewage system. An object of the present invention is to provide an aqueous resin dispersion for coating materials and a coating material for water and sewage lining materials.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include a polymer obtained by emulsion polymerization of a polymerizable monomer mixture having a specific composition, and has a minimum film formation temperature in a specific range. It has been found that the above problems can be solved by using an aqueous resin dispersion, and the present invention has been completed.

That is, the present invention is as follows.
[1]
Reactive surfactant with 95% by mass or more of polymerizable monomer having water solubility of less than 0.5 g / 100 g of water, 0.1% by mass or more and less than 1.0% by mass of alkoxysilane group-containing polymerizable monomer And a polymer obtained by emulsion polymerization of a polymerizable monomer mixture containing
The minimum film formation temperature is 5 ° C or less,
An aqueous resin dispersion for water and sewage lining material paints, containing a component that is liquid at 20 ° C. and has a boiling point of 160 ° C. or more in an amount of 5 parts by mass or less based on 100 parts by mass of the polymer.
[2]
The aqueous resin dispersion for water and sewage lining material paints according to [1], wherein the calculated glass transition temperature of the polymer is -30 ° C or higher and 10 ° C or lower.
[3]
The aqueous polymer dispersion for water and sewage lining material paints according to [1] or [2], wherein the polymer is a polymer modified with a compound represented by the following general formula (1).
_{^{(R 1) n -Si- (R}} 2) (4-n) (1)
(In Formula (1), n is an integer of 0 or more and 3 or less. R ¹ is hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 5 or more carbon atoms. Represents a cycloalkyl group having 6 or less, n R ^{1 s} may be the same or different, and R ² represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. (4-n) R ^{2 s} may be the same or different.)
[4]
In the formula (1), n is an aqueous resin dispersion for water and sewage lining material paints according to [3], which is an integer of 1 or more and 3 or less.
[5]
Any one of [1] to [4], containing 40% by mass or more of cyclohexyl methacrylate as a polymerizable monomer having a water solubility of less than 0.5 g / 100 g of water with respect to 100% by mass of the polymerizable monomer mixture. An aqueous resin dispersion for water and sewage lining material paints as described in 1.
[6]
A paint for water and sewage lining materials, comprising the aqueous resin dispersion for water and sewage lining material paints according to any one of [1] to [5].

  According to the present invention, an aqueous resin dispersion for a water and sewage lining material paint and a water and sewage lining material paint excellent in workability, film forming property, water resistance and sulfuric acid resistance when used for repairing an existing water and sewage system. Can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

  The aqueous resin dispersion for water and sewage lining material paints of the present embodiment has a water solubility of 95% by mass or more with a water solubility of less than 0.5 g / 100 g of water and an alkoxysilane group-containing polymerizable monomer of 0.1%. Polymers obtained by emulsion polymerization of a polymerizable monomer mixture containing at least mass% and less than 1.0 mass% and a reactive surfactant (hereinafter referred to as “polymer (A)”, “component (A)”) The minimum film formation temperature is 5 ° C. or lower. Furthermore, the aqueous resin dispersion for water and sewage lining material paints of this embodiment is a liquid at 20 ° C. and a component having a boiling point of 160 ° C. or more in an amount of 5 parts by mass or less with respect to 100 parts by mass of the polymer. contains. Because of this construction, the water-based resin dispersion for water and sewage lining material paints of this embodiment has excellent workability, film formability, water resistance and sulfuric acid resistance when used for repairing existing water and sewage systems. Excellent. The “aqueous resin dispersion” in the present embodiment means that the resin component is maintained in a dispersed state in water.

  The aqueous resin dispersion for water and sewage lining material paints of this embodiment contains 95% by mass or more of a polymerizable monomer having a solubility of less than 0.5 g / 100 g of water. Therefore, excellent water resistance can be imparted to the coating film itself, and excellent sulfuric acid resistance can be realized when used for repairing an existing water and sewage system. The solubility is a value measured at 25 ° C.

  Examples of the polymerizable monomer having a water solubility of less than 0.5 g / 100 g of water in the present embodiment include, but are not limited to, for example, styrene (0.03 g), cyclohexyl methacrylate (0.01 g or less), and methacrylic acid. n-butyl (0.04 g), t-butyl methacrylate (0.05 g), i-butyl methacrylate (0.04 g), 2-ethylhexyl methacrylate (0.01 or less), lauryl methacrylate (0.01 g) ), N-butyl acrylate (0.20 g), 2-ethylhexyl acrylate (0.01 g), and the like. These may be used alone or in combination of two or more. From the viewpoint of water resistance and various chemical resistances, it is preferable to include cyclohexyl methacrylate as the polymerizable monomer, and it is more preferable to include both cyclohexyl methacrylate and 2-ethylhexyl acrylate. In addition, the content of cyclohexyl methacrylate with respect to 100% by mass of the polymerizable monomer mixture is preferably 30% by mass or more and more preferably 40% by mass or more from the viewpoint of water resistance. Furthermore, from the viewpoint of film formability, it is preferably 60% by mass or less, and more preferably 50% by mass or less.

  The content ratio of the alkoxysilane group-containing polymerizable monomer to the total amount (100% by mass) of the polymerizable monomer mixture used for the emulsion polymerization of the water-based resin dispersion for water and sewage lining materials is the water resistance of the coating film. From the viewpoint of sulfuric acid resistance, it is 0.1% by mass or more and less than 1.0% by mass, preferably 0.5% by mass or more and less than 1.0% by mass, more preferably 0.7% by mass or more and 1% by mass. Less than 0.0% by mass. When the content ratio of the alkoxysilane group-containing polymerizable monomer is less than 1.0% by mass, the degree of cross-linking of the aqueous resin dispersion for water and sewage lining material paint can be adjusted to an appropriate range. Becomes better. Therefore, it can prevent that a defect is made in a coating film and can implement | achieve the outstanding sulfuric acid resistance when it uses for repair of the existing water and sewage.

  The alkoxysilane group-containing polymerizable monomer in the present embodiment is not particularly limited as long as it is a polymerizable monomer containing an alkoxysilane group. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β -Methoxyethoxy) silane, vinylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropylmethyldimethoxysilane, gamma-methacrylic Examples include roxypropyltriethoxysilane and γ-methacryloxypropylmethyldiethoxysilane. These may be used alone or in combination of two or more. Among these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropylmethyldiethoxysilane are preferable. Of these, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are more preferable.

  In this embodiment, the polymerizable monomer mixture is a polymerizable monomer having a water solubility of less than 0.5 g / 100 g of water or another polymerizable monomer copolymerizable with an alkoxysilane group-containing polymerizable monomer. May contain body. Examples of other polymerizable monomers include, but are not limited to, for example, (meth) acrylic acid esters, hydroxyl group-containing polymerizable monomers, carboxylic acid group-containing polymerizable monomers, and other polymerizations. Ionic monomers.

  The (meth) acrylic acid ester in the present embodiment is not limited to the following, but, for example, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms and an ethylene oxide group having 1 to 100 carbon atoms. (Poly) oxyethylene mono (meth) acrylate, (poly) oxypropylene mono (meth) acrylate having a propylene oxide group of 1 to 100, (meth) acrylic acid hydroxyalkyl ester having an alkyl group of 1 to 18 carbon atoms, (Poly) oxyethylene di (meth) acrylate having 1 to 100 ethylene oxide groups may be mentioned. These may be used alone or in combination of two or more.

  In the present embodiment, the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms and having a water solubility of 0.5 g / 100 g or more of water is not limited to the following, but for example, methyl methacrylate (1 .72 g), ethyl acrylate (1.50 g), and the like.

  The hydroxyl group-containing polymerizable monomer in the present embodiment is not limited to the following, but examples thereof include 2-hydroxyethyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Examples include acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate is preferable.

  The carboxylic acid group-containing polymerizable monomer in the present embodiment is not limited to the following, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, maleic anhydride and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, acrylic acid and methacrylic acid are preferable.

  In other polymerizable monomers in the present embodiment, as the polymerizable monomer other than the (meth) acrylic acid ester, the hydroxyl group-containing polymerizable monomer and the carboxylic acid group-containing polymerizable monomer described above, Listed are polymerizable monomers other than these and polymerizable monomers capable of polymerizing with a polymerizable monomer having an aqueous solubility of less than 0.5 g / 100 g of water or an alkoxysilane group-containing polymerizable monomer. There is no particular limitation. Specific examples include vinyl esters such as vinyl acetate, vinyl propionate and vinyl persuccinate; vinyl cyanides such as (meth) acrylonitrile; vinyl halides such as vinyl chloride and vinylidene chloride; olefins such as ethylene. Is mentioned. Further, various functional monomers such as (meth) acrylamide, vinyl pyrrolidone, glycidyl (meth) acrylate, N-methylol acrylamide, N-butoxymethyl acrylamide, and divinylbenzene are also included. One of the above may be used alone, or two or more may be used in combination.

  The reactive surfactant in the present embodiment is not particularly limited as long as it is a surfactant having polymerization activity. For example, a reactive anionic surfactant or a reactive nonionic surfactant can be used. Specific examples of the reactive anionic surfactant include, but are not limited to, “Adekalia Soap SE-1025A”, “Adekalia Soap SR-1025”, “Adekalia Soap SR-3025” (manufactured by ADEKA). “AQUALON KH-1025”, “AQUALON HS-1025”, “AQUALON BC-1025”, “AQUALON BC-2020” (Daiichi Kogyo Seiyaku Co., Ltd.), “Latemul PD-104” (manufactured by Kao), “ ELEMINOL JS-20 "," ELEMINOL RS-3000 "(manufactured by Sanyo Chemical Co., Ltd.) and the like. Specific examples of the reactive nonionic surfactant include, but are not limited to, “Adekalia Soap ER-10”, “Adekalia Soap ER-20”, “Adekalia Soap ER-30”, “Adekalia Soap” "ER-40", "Adekaria soap NE-10", "Adekaria soap NE-20", "Adekaria soap NE-30" (manufactured by ADEKA), "Aquaron RN-20", "Aquaron RN-30" "AQUALON RN-50" (Daiichi Kogyo Seiyaku Co., Ltd.).

The aqueous resin dispersion for water and sewage lining material paints of this embodiment has a minimum film forming temperature of 5 ° C. or lower. When the minimum film forming temperature is 5 ° C. or lower, the film forming property as a lining material paint is maintained in a good state, and it is possible to prevent the coating film from cracking and deteriorating.
The minimum film formation temperature can be adjusted, for example, by the following method. By lowering the glass transition temperature of the polymer (A), the minimum film formation temperature can be lowered. In addition, by making the particle structure a core-shell structure, even if the glass transition temperature of the entire resin dispersion is the same, the minimum film-forming temperature can be reduced by lowering the glass transition temperature of the monomer component constituting the shell portion. Can be lowered. Further, the minimum film formation temperature can be controlled by various methods, for example, the minimum film formation temperature can be lowered by reducing the content of the alkoxysilane group-containing polymerizable monomer. Among these, it is preferable to adjust the glass transition temperature of a polymer (A) from the point of adjustment effect.

The water-based resin dispersion for water and sewage lining material paints of this embodiment has a calculated glass transition temperature of the polymer (A) of −30 ° C. or more and 10 ° C. or less from the viewpoint of adjusting the minimum film forming temperature to a preferable range. Is preferred. When the calculated glass transition temperature is 10 ° C. or lower, the minimum film forming temperature can be adjusted to a preferable range, and the film forming property of the lining material tends to be maintained in a better state. Moreover, it exists in the tendency for the fall of the water resistance of a lining material to be suppressed more because a calculation glass transition temperature is -30 degreeC or more. In this embodiment, the “calculated glass transition temperature” is determined by the following formula from the glass transition temperature and copolymerization ratio of the homopolymer of each monomer. Note that the alkoxysilane group-containing polymerizable monomer is not included in the calculation of the calculated glass transition temperature because it has crosslinkability and is used in a small amount. Also, the reactive surfactant is not included in the calculation of the calculated glass transition temperature.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ...
(Tg: Calculated glass transition temperature (K) of copolymer consisting of monomers 1, 2,...; W1, W2...: Copolymer of monomer 1, monomer 2,... Mass fraction (W1 + W2 +... = 1); Tg1, Tg2...: Glass transition temperature (K) of homopolymer of monomer 1, monomer 2,.

The Tg (K) of the homopolymer used in the above formula is described in, for example, the polymer handbook (Jhon Willy & Sons). The numerical values used in this embodiment will be exemplified below. The value in parentheses indicates the Tg of the homopolymer. Polystyrene (373K), polymethyl methacrylate (378K), poly (n-butyl acrylate) (228K), poly (2-ethylhexyl acrylate) (218K), polyacrylic acid (360K), polymethacrylic acid (417K), polyacrylonitrile ( 369K), 2-hydroxyethyl polyacrylate (258K), poly 2-hydroxyethyl methacrylate (328K).
When the copolymerization ratio is unknown, the calculated glass transition temperature is calculated by the above formula after obtaining the copolymerization ratio by pyrolysis-GCMS and NMR.

  Table 1 shows the water solubility of typical polymerizable monomers and the Tg of the homopolymer.

  The aqueous resin dispersion for water and sewage lining material paints of this embodiment is a liquid at 20 ° C. and a component having a boiling point of 160 ° C. or more in 5 parts by mass or less with respect to 100 parts by mass of the polymer (A). contains. As a result, in applications where it is difficult to carry out a heating process, such as for repairing existing water and sewage systems, such components remain in the water and sewage lining material paint, and elution into water during use of water and sewage systems Can be prevented. The content of the component is preferably 4% by mass or less, more preferably 3% by mass or less, and the component may not be contained.

The components that are liquid at 20 ° C. and have a boiling point of 160 ° C. or higher are not limited to the following, but examples include film forming aids and antifreezing agents.
The film forming aid in the present embodiment is not limited to the following, but for example, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, 2, 2, 4-trimethyl-1,3-butanediol isobutyrate, diisopropyl glutarate, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, 2,2,4-trimethyl-1,3-pentanediol 1-isobutyrate, diethylene glycol monobutyl Chromatography ether acetate, ethylene glycol mono-2-ethylhexyl ether, dibutyl phthalate, diethyl adipate, adipic acid diisobutyl.
The antifreezing agent in the present embodiment is not limited to the following, and examples thereof include propylene glycol and ethylene glycol.

  The aqueous resin dispersion for water and sewage lining material paints of the present embodiment is composed of a polymerizable monomer having a water solubility of less than 0.5 g / 100 g of water, an alkoxysilane group-containing polymerizable monomer, and other polymerizable as required. It is obtained by emulsion polymerization of a monomer. The mode of emulsion polymerization is not particularly limited, and a conventionally known method can be used.

  The aqueous resin dispersion for water and sewage lining material paints in this embodiment may contain a surfactant other than the reactive surfactant described above. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants.

  Nonionic surfactants in the present embodiment are not limited to the following, for example, polyoxyethylene alkyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene distyrenated phenyl ether, sorbitan fatty acid ester, polyoxy Examples include ethylene fatty acid esters and polyoxyethylene-polyoxypropylene block copolymers. These may be used alone or in combination of two or more. Among these, polyoxyethylene alkyl ether and polyoxyethylene distyrenated phenyl ether are preferable.

  The anionic surfactant in the present embodiment is not limited to the following, but examples thereof include fatty acid salts such as sodium lauryl sulfate, higher alcohol sulfate esters, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polyoxy Examples thereof include ethylene alkyl ether sulfate, polyoxyethylene polycyclic phenyl ether sulfate, polyoxynonyl phenyl ether sulfonate, and polyoxyethylene-polyoxypropylene glycol ether sulfate.

  The cationic surfactant in the present embodiment is not limited to the following, and examples thereof include alkylamine salts and quaternary ammonium salts.

  The amphoteric surfactant in the present embodiment is not limited to the following, and examples thereof include alkylbetaines and alkylamine oxides.

  The polymer surfactant in the present embodiment is not limited to the following, and examples thereof include (modified) polyvinyl alcohol.

  The various surfactants described above may be used alone or in combination of two or more.

In the water-based resin dispersion for water and sewage lining material paints of the present embodiment, the polymer (A) is also referred to as a compound containing Si (hereinafter, also referred to as “Si-containing compound”) from the viewpoint of improving adhesiveness with an inorganic substance. ) Is preferably modified. From the same viewpoint as above, the Si-containing compound used for modification is more preferably a compound represented by the following general formula (1).
_{^{(R 1) n -Si- (R}} 2) (4-n) (1)
(In Formula (1), n is an integer of 0 or more and 3 or less. R ¹ is hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 5 or more carbon atoms. Represents a cycloalkyl group having 6 or less, wherein n R ^{1 s} may be the same or different, and R ² represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or Represents a hydroxyl group. (4-n) R ^{2 s} may be the same or different.)

R ¹ in Formula (1) is preferably each independently a methyl group or a phenyl group. R ² is preferably each independently a methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group, or hydroxyl group.

  In the aqueous resin dispersion for water and sewage lining material paints of this embodiment, from the viewpoint of polymerization stability of the aqueous resin dispersion for water and sewage lining material paints, n is an integer of 1 to 3 in the above formula (1). More preferably, the polymer (A) is modified with a Si-containing compound.

  The Si-containing compound in the present embodiment includes at least one of a silane compound (I) in which n = 0 in the above formula (1) and a silane compound (II) in which n = 1 in the above formula (1). Is more preferable, and from the viewpoint of polymerization stability when obtaining an aqueous resin dispersion for water and sewage lining materials, it is more preferable to include a silane compound (II).

R ² in formula (1) of the silane compound (I) is preferably independently a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Preferable specific examples of the silane compound (I) include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination of two or more.

In formula (1) of the silane compound (II), R ¹ is preferably a methyl group or a phenyl group, and R ² is each independently a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group. Is preferred. Preferable specific examples of the silane compound (II) include methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, and isobutyltrimethoxysilane. These may be used alone or in combination of two or more. Of these, methyltrimethoxysilane is more preferable.

  The water-based resin dispersion for water and sewage lining material paints in this embodiment is a silane compound having a cyclic silane compound and n = 2 in the above formula (1) as a Si-containing compound from the viewpoint of improving mechanical properties when used as a paint It is preferable to contain at least one compound (III). More preferably, it includes at least one of cyclic silane and silane compound (III) and at least one of silane compound (I) and silane compound (II), and more preferably, cyclic silane compound and silane. It contains at least one compound (III) and a silane compound (II). In particular, by using any one of a cyclic silane compound and a silane compound (III) in combination with the silane compound (II), the crosslinking density of the component (A) that is a polymer tends to be controlled low. is there. As a result, there is a tendency that the mechanical properties of the coating film formed by the water and sewage lining material paint of the present embodiment described later can be further improved.

  Specific examples of the cyclic silane compound in the present embodiment are not limited to the following, but examples include octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane. These may be used alone or in combination of two or more.

  Specific examples of the silane compound (III) are not limited to the following, and examples thereof include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and methylphenyldimethoxysilane. These may be used alone or in combination of two or more. Of these, dimethyldimethoxysilane is more preferable.

  The Si-containing compound may further include at least one selected from the group consisting of a linear siloxane having a hydrolytic group, an alkoxysilane oligomer, and a silane compound (IV) in which n = 3 in the above formula (1). .

  The linear siloxane having a hydrolyzable group in the present embodiment is not limited to the following, and examples thereof include compounds represented by the following general formulas (i), (ii), and (iii).

（式（ｉ）〜（ｉｉｉ）中、Ｒ³は、各々独立に、水素、炭素数１以上１６以下のアルキル基、炭素数６以上１０以下のアリール基、炭素数５以上６以下のシクロアルキル基、炭素数１以上１０以下のアクリル酸アルキル基、又は炭素数１以上１０以下のメタクリル酸アルキル基を表す。Ｒ⁴は、各々独立に、炭素数１以上８以下のアルコキシ基、アセトキシ基、水酸基、エポキシ基、アルキレンオキサイド基、又はポリアルキレンオキサイド基を表す。ｍは、１以上９９９以下の整数である。）

(In formulas (i) to (iii), each R ³ independently represents hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cycloalkyl having 5 to 6 carbon atoms. Group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, each of R ⁴ independently represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, Represents a hydroxyl group, an epoxy group, an alkylene oxide group, or a polyalkylene oxide group, and m is an integer of 1 to 999.

R ¹ in formula (1) of the silane compound (IV) is preferably a methyl group or a phenyl group. R ² in formula (1) of the silane compound (IV) is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, or a hydroxyl group.

  Preferable specific examples of the silane compound (IV) in the present embodiment include triphenylethoxysilane and trimethylmethoxysilane. These may be used alone or in combination of two or more.

  The Si-containing compound in the present embodiment further includes, for example, chlorosilane compounds such as methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, and diphenylchlorosilane as other silane compounds than the above-described silane compounds. be able to.

In the present embodiment, the use of an aqueous resin dispersion for water and sewage lining material paints containing a polymer (A) modified with a Si-containing compound further improves the adhesion to inorganic substances, water resistance, and sulfuric acid resistance. Tend to be able to. The presence of the aqueous resin dispersion for water and sewage lining material paints containing the polymer (A) modified with the Si-containing compound is determined by ²⁹ Si-NMR ( ²⁹ Si nuclear magnetic resonance spectrum) and / or ¹ H-NMR (proton nucleus). Magnetic resonance spectrum). For example, a condensate of silane compound (II) usually shows a signal at −40 ppm to −80 ppm in a chemical shift of ²⁹ Si-NMR.

  In this embodiment, it is preferable to use 0.1 mass part or more and 10.0 mass parts or less of Si containing compound with respect to the total amount (100 mass parts) of the polymer (A) before modification | denaturation. When it is in the above range, a more stable aqueous resin dispersion for water and sewage lining material paints tends to be obtained. In addition, when a Si-containing compound is used, it is easy to adjust the degree of crosslinking of the aqueous resin dispersion for water and sewage lining material paints, and it is also possible to adjust the film formability.

  Although the average particle diameter of the water-based resin dispersion for water and sewage lining material paints of this embodiment is not specifically limited, Preferably it is 30 nm or more and 500 nm or less. The average particle diameter of the aqueous resin dispersion can be measured by the method described in Examples described later.

  The solid content of the aqueous resin dispersion for water and sewage lining material paints of this embodiment is not particularly limited, but is preferably 30% by mass or more and 65% by mass or less. Solid content can be measured by the method as described in the Example mentioned later.

  As described above, the emulsion polymerization method is employed as the method for producing the aqueous resin dispersion for water and sewage lining material paints in the present embodiment. The method such as the reaction conditions for the emulsion polymerization is not limited to the following, but as a preferred method, in water, in the presence of an emulsifier, a polymerization initiator and the like, the pH is 4 or less, usually 60 ° C. or more. A method of emulsion polymerization of a polymerizable monomer at 90 ° C. or lower is exemplified. In the emulsion polymerization, a method of repeating this emulsion polymerization step once or a plurality of times is mentioned.

  Specific examples of the polymerization method of emulsion polymerization in the present embodiment are not limited to the following, but a monomer batch charging method in which polymerizable monomers are batch charged; a polymerizable monomer is continuously dropped. Monomer dropping method; a pre-emulsion method in which a polymerizable monomer, water and an emulsifier are mixed and emulsified in advance, and these are added dropwise; and a combination of these. The method for using the polymerization initiator is not particularly limited. Further, when using the above-described Si-containing compound, the use method thereof includes a condensation reaction of a hydrolyzable Si-containing compound (hereinafter also referred to as “hydrolyzable silane”) and a polymerizable single group having an unsaturated group. Emulsion polymerization method in which radical polymerization of an unsaturated monomer proceeds simultaneously with radical polymerization of a monomer (hereinafter also referred to as "unsaturated monomer") or preceded by a condensation reaction of hydrolyzable silane A method in which the condensation reaction of hydrolyzable silane proceeds after the radical polymerization of the unsaturated monomer proceeds.

  As a polymerization initiator in this embodiment, although not limited to the following, the radical initiator generally used can be used. The radical polymerization initiator is one that generates radicals by heat, a reducing substance or the like to cause addition polymerization of a polymerizable monomer. The radical polymerization initiator is not limited to the following, and examples thereof include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. More specifically, but not limited to, for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2,2-azobisiso Examples include butyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, and 2,2-azobis (2,4-dimethylvaleronitrile). These may be used alone or in combination of two or more. Among these, water-soluble ones are preferable. If further acceleration of the polymerization rate or reaction at a low temperature is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfoxylate salt, etc. should be used in combination with a radical polymerization initiator. Is preferred.

In the emulsion polymerization in the present embodiment, a molecular weight modifier can be used as necessary. The molecular weight modifier is not limited to the following, and examples thereof include dodecyl mercaptan and butyl mercaptan. Although the usage-amount of a molecular weight modifier is not specifically limited, It is preferable that it is 2 mass% or less with respect to the total amount (100 mass%) of a polymerizable monomer.
In the present embodiment, from the viewpoint of further improving the long-term dispersion stability of the long-term aqueous resin dispersion for water and sewage lining material paints, it is preferable to control the pH after the polymerization in the range of 5 to 10. Specifically, basic substances such as basic organic compounds such as amines such as ammonia and dimethylaminoethanol; basic inorganic compounds such as alkali metal salts such as sodium hydroxide and potassium hydroxide, etc. By using after polymerization, the pH can be adjusted in the range of 5 or more and 10 or less.

  The curing catalyst for film formation that can be used after the completion of emulsion polymerization in the present embodiment is not limited to the following, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, Metal salts of organic acids such as tin laurate, iron octylate, lead octylate and tetrabutyl titanate; amine compounds such as n-hexylamine and 1,8-diazabicyclo [5,4,0] -7-undecene It is done. When these curing catalysts are not water-soluble, it is preferable to emulsify the curing catalyst with an emulsifier and water before use.

  The water and sewage lining material paint of the present embodiment includes the aqueous resin dispersion for water and sewage lining material paint of the present embodiment. The water and sewage lining material paint may further include other components added and blended with a normal aqueous resin dispersion or the like within the range of the effect. Examples of such other components include, but are not limited to, thickeners, antifoaming agents, dyes, and preservatives. These other components may be used individually by 1 type, and may use 2 or more types together.

  The thickener in the present embodiment is not limited to the following, but examples thereof include polymer dispersion stabilizers such as polyvinyl alcohol (including partially saponified polyvinyl acetate), methyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, and the like. Examples include polyether-based and polycarboxylic acid-based thickeners.

  The water and sewage lining material paint of this embodiment can further contain a filler and an additive. In this case, the water and sewage lining material paint of the present embodiment can be suitably used as a water and sewage lining material, and can exhibit excellent water resistance, sulfuric acid resistance and adhesiveness.

  The filler used in the water and sewage lining material paint of the present embodiment is not limited to the following, and examples thereof include inorganic or organic pigments. For example, examples of the inorganic pigment include various metal oxides such as magnesium, calcium, zinc, barium, titanium, aluminum, antimony, and lead; hydroxides, sulfides, carbonates, sulfates, and silicate compounds. Specific examples of the compound include calcium carbonate, kaolin, talc, titanium dioxide, aluminum hydroxide, silica, gypsum, barite powder, alumina white, and satin white. Examples of organic pigments include solid polymer fine powders such as polystyrene, polyethylene, and polyvinyl chloride.

  Additives used in the water and sewage lining material paint of the present embodiment are not limited to the following, but include, for example, water reducing agents and fluidizing agents (for example, polycarboxylic acid type, melamine sulfonic acid type, naphthalene sulfonic acid type) , Lignin sulfonic acid type), shrinkage reducing agent (for example, glycol ether type, polyether type), cryogenic agent (for example, calcium chloride, silicate), waterproofing agent (for example, stearic acid, silicon type), rust inhibitor ( For example, phosphate, nitrite), viscosity modifier (eg, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol), setting modifier (eg, phosphate), swelling agent (eg, ettringite, lime), colorant (For example, iron oxide, chromium oxide), antifoaming agent (for example, silicon-based, mineral oil-based), reinforcing material (for example, steel fiber, Lath fibers, synthetic fibers), surfactants (for example, anions, nonions, cationic series), thickeners, leveling agents, film-forming aids, solvents, plasticizers, dispersants, water resistance agents, and lubricants. .

  Hereinafter, the present embodiment will be described in detail by way of specific examples and comparative examples, but the present embodiment is not limited by these examples and comparative examples unless they exceed the gist thereof. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples are based on mass standards. Various physical properties and evaluations in Examples and Comparative Examples were measured and evaluated as follows.

<Polymerization stability>
In the polymerization reaction, the polymerization stability was determined to be good when there was no aggregate by visually confirming the presence or absence of the aggregate after the polymerization reaction.

<Calculated glass transition temperature>
About the water-based resin dispersion for water and sewage lining material paints, the calculated glass transition temperature of the polymer (A) (indicated as “calculated Tg” in Table 2) is the glass transition temperature of the monomer homopolymer and Based on the copolymerization ratio, it was calculated by the following formula.
1 / Tg = W1 / Tg1 + W2 / Tg2 + ...
(Tg: Calculated glass transition temperature (K) of copolymer consisting of monomers 1, 2,...; W1, W2...: Copolymer of monomer 1, monomer 2,... Mass fraction (W1 + W2 +... = 1); Tg1, Tg2...: Glass transition temperature (K) of homopolymer of monomer 1, monomer 2,.

<Average particle size>
Using a water-based resin dispersion for water and sewage lining material paint as a sample, the volume average particle size measured with a laser diffraction particle size distribution meter (manufactured by Leeds and Northrup, Microtrac particle size distribution meter “UPA150”), It was set as the average particle diameter (nm) of the aqueous resin dispersion.

<Solid content>
Using an aqueous resin dispersion for water and sewage lining material paint as a sample, 1 g of the aqueous resin dispersion was accurately weighed on an aluminum dish, dried at 105 ° C. for 3 hours with a constant temperature dryer, and 30 minutes in a desiccator containing silica gel. After standing to cool, it was weighed accurately. The ratio obtained by dividing the mass after drying by the mass before drying was defined as the solid content (%).

<Minimum deposition temperature (MFT)>
A water-based resin dispersion for water and sewage lining materials is coated on an aluminum plate placed on a thermal gradient tester with a 0.1 mm applicator and dried. The film temperature (MFT) was used.

<Water and sewage lining material paint>
Water-based resin dispersion for water and sewage lining materials paint 100.00 parts by mass BYK-420 (Thickener: manufactured by BYK) 0.06 parts by mass BYK-425 (thickener: manufactured by BYK) 0.06 parts by mass BYK -028 (antifoaming agent: manufactured by BYK) 0.06 parts by mass The above mixture was stirred until uniform to obtain a water and sewage lining material paint.

<Mass change rate of coating film>
Water and sewage lining material paint was applied to a glass plate to a thickness of 250 μm, formed at room temperature, then cut into 5 cm × 5 cm, and further left at 50 ° C. for 1 week to test Used as a body. The mass of the obtained specimen was measured. Moreover, the mass was measured also about what dipped the test body in the water of room temperature or 10% sulfuric acid aqueous solution for 7 days, and wiped off the water of the test body surface after that. Based on the following formula, the water absorption rate before and after immersion (weight change rate of the coating film) was calculated.
Water Absorption Rate (%) = (Mass of Specimen after Soaking in Water−Mass of Specimen before Soaking) / Mass of Specimen before Soaking × 100

<Measurement of sulfuric acid resistance>
On the entire surface of a mortar plate of 70 mm × 70 mm × 20 mm specified in JIS K-5600, 400 parts by mass / m ^{2 of} water and sewage lining material paint was applied by brushing and cured at room temperature for 1 week. Then, it was immersed in a 10% sulfuric acid aqueous solution for 4 weeks, and the appearance was observed. Evaluation was performed according to the following criteria.
◎: No change ○: Almost no change, but abnormal in edge, etc. △: Partially abnormal ×: Abnormal

<Water-based resin dispersion 1 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 480.0 parts by mass of cyclohexyl methacrylate, 500.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of γ-methacryloxypropyltrimethoxysilane, “Adekalia” An emulsified mixed solution of 40.0 parts by mass of soap SR-1025, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained water-based resin dispersion 1 for water and sewage lining material paints had an average particle diameter of 131 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 2 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 400.0 parts by mass of styrene, 580.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of γ-methacryloxypropyltrimethoxysilane, “Adekaria soap SR −1025 ”40.0 parts by mass, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water were allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 2 for water and sewage lining material paints had an average particle diameter of 128 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 3 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 480.0 parts by mass of cyclohexyl methacrylate, 500.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of γ-methacryloxypropyltrimethoxysilane, methyltrimethoxy Emulsification of 10.0 parts by mass of silane, 10.0 parts by mass of dimethyldimethoxysilane, 40.0 parts by mass of “ADEKA rear soap SR-1025”, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water The mixed solution was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 3 for water and sewage lining material paints had an average particle diameter of 132 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 4 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 480.0 parts by weight of cyclohexyl methacrylate, 500.0 parts by weight of 2-ethylhexyl acrylate, 20.0 parts by weight of methacrylic acid, 5.0 parts by weight of γ-methacryloxypropyltrimethoxysilane, “Adekalia An emulsified mixed solution of 40.0 parts by mass of soap SR-1025, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 4 for water and sewage lining material paints had an average particle diameter of 129 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 5 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 600.0 parts by weight of cyclohexyl methacrylate, 380.0 parts by weight of 2-ethylhexyl acrylate, 20.0 parts by weight of methacrylic acid, 10.0 parts by weight of γ-methacryloxypropyltrimethoxysilane, “Adekalia An emulsified mixed solution of 40.0 parts by mass of soap SR-1025, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained water-based resin dispersion 5 for water and sewer lining material paints had an average particle diameter of 130 nm and MFT of 20 ° C. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 6 for water and sewage lining material paint>
Into a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer, 371.7 parts by mass of water and 13.3 parts by mass of “New Coal 707SF” (made by Nippon Emulsifier Co., Ltd .; anionic surfactant) are charged. The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 400.0 parts by mass of styrene, 580.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of γ-methacryloxypropyltrimethoxysilane, “Newcol 707SF” An emulsified mixed solution of 33.3 parts by mass, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate and 526.7 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 6 for water and sewage lining material paints had an average particle size of 130 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 7 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 430.0 parts by weight of methyl methacrylate, 550.0 parts by weight of 2-ethylhexyl acrylate, 20.0 parts by weight of methacrylic acid, 10.0 parts by weight of γ-methacryloxypropyltrimethoxysilane, “Adekalia An emulsified mixed solution of 40.0 parts by mass of soap SR-1025, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 7 for water and sewage lining material paints had an average particle size of 135 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Water-based resin dispersion 8 for water and sewage lining material paint>
In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank, and a thermometer, 377.0 parts by mass of water, “ADEKA rear soap SR-1025” (manufactured by ADEKA; reactive anionic surfactant) 8.0 mass The temperature in the reaction vessel was raised to 80 ° C., and 15 parts by mass of a 2% aqueous solution of ammonium persulfate was added. Five minutes later, 480.0 parts by mass of cyclohexyl methacrylate, 500.0 parts by mass of 2-ethylhexyl acrylate, 20.0 parts by mass of methacrylic acid, 20.0 parts by mass of γ-methacryloxypropyltrimethoxysilane, “Adekalia An emulsified mixed solution of 40.0 parts by mass of soap SR-1025, 50.0 parts by mass of a 2% aqueous solution of ammonium persulfate, and 520.0 parts by mass of water was allowed to flow into the reaction vessel over 240 minutes. During the inflow, the temperature of the reaction vessel was maintained at 80 ° C. After completion of the inflow, the temperature of the reaction vessel was maintained at 80 ° C. for 60 minutes and then cooled, adjusted to pH 7.5 with 25 mass% aqueous ammonia, and then adjusted to a solid content ratio of 50.0 mass% with water. The obtained aqueous resin dispersion 8 for water and sewage lining material paints had an average particle diameter of 129 nm and MFT of 3 ° C. or lower. There was no generation of aggregates and the polymerization stability was good.

<Example 1>
Using the water-based resin dispersion 1 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Example 2>
Using the water-based resin dispersion 2 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Example 3>
Using the water-based resin dispersion 3 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Example 4>
Using the water-based resin dispersion 4 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Comparative Example 1>
Using the water-based resin dispersion 5 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Comparative example 2>
Using the water-based resin dispersion 6 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Comparative Example 3>
Using the water-based resin dispersion 7 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

<Comparative example 4>
Using the water-based resin dispersion 8 for water and sewage lining material paint, the physical properties of the lining material paint were evaluated by the above blending and testing. The results are shown in Table 2.

  In Table 2, St represents styrene, MMA represents methyl methacrylate, CHMA represents cyclohexyl methacrylate, 2-EHA represents 2-ethylhexyl acrylate, and MAA represents methacrylic acid.

  The aqueous resin dispersion for water and sewage lining material paints according to the present invention can be suitably used for applications such as water and sewage lining material paints.

Claims (5)

Reactive surfactant with 95% by mass or more of polymerizable monomer having water solubility of less than 0.5 g / 100 g of water, 0.1% by mass or more and less than 1.0% by mass of alkoxysilane group-containing polymerizable monomer And a polymer obtained by emulsion polymerization of a polymerizable monomer mixture containing
As a polymerizable monomer having a water solubility of 0.5 g / less than 100 g of water with respect to 100% by mass of the polymerizable monomer mixture, 40% by mass or more of cyclohexyl methacrylate is included,
The minimum film formation temperature is 5 ° C or less,
A component that is liquid at 20 ° C. and has a boiling point of 160 ° C. or more is contained in an amount of more than 0 parts by mass and not more than 5 parts by mass with respect to 100 parts by mass of the polymer, or does not contain the component. Water-based resin dispersion for coating materials.   The aqueous resin dispersion for water and sewage lining material paints according to claim 1, wherein the calculated glass transition temperature of the polymer is -30 ° C or higher and 10 ° C or lower. The aqueous polymer dispersion for water and sewage lining material paint according to claim 1 or 2, wherein the polymer is a polymer modified with a compound represented by the following general formula (1).
_{^{(R 1) n -Si- (R}} 2) (4-n) (1)
(In Formula (1), n is an integer of 0 or more and 3 or less. R ¹ is hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 5 or more carbon atoms. Represents a cycloalkyl group having 6 or less, n R ^{1 s} may be the same or different, and R ² represents an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. (4-n) R ^{2 s} may be the same or different.)   In the said Formula (1), n is an aqueous resin dispersion for water and sewage lining material coating materials of Claim 3 which is an integer greater than or equal to 1 and 3 or less. A paint for water and sewage lining materials, comprising the aqueous resin dispersion for water and sewage lining material paints according to any one of claims 1 to 4 .