JP2018083936A - Aqueous lining material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous lining material composition excellent in anticorrosion properties and adhesiveness to concrete.SOLUTION: The aqueous lining material composition contains: a (co)polymer (A) in which the total number of carboxyl groups and hydroxyl groups is at least two; a crosslinking agent having at least two functional groups capable of reacting with (A); a filler; and water. The (co)polymer preferably contains, as constituent monomers, an unsaturated monomer (a1) having carboxyl groups and/or an unsaturated monomer (a2) having hydroxyl groups and an unsaturated monomer (a3) other than (a1) and (a2).SELECTED DRAWING: None

Description

  The present invention relates to an aqueous lining material composition. More particularly, the present invention relates to an aqueous lining material composition suitable for water and sewage.

  Water and sewage facilities are generally lined with concrete surfaces for the purpose of waterproofing and anticorrosion. Conventionally, as a lining material, a method of forming a cured film by applying a mixture of an epoxy resin and an amine (Patent Document 1) is known.

Japanese Patent Laying-Open No. 2005-307076

However, since the construction of the lining material is performed in a semi-enclosed space, the technique using an amine as in Patent Document 1 has a problem that the skin of the operator may be struck, and a solution to that problem is required. It was.
The object of the present invention is to solve the above-mentioned problems and to provide an aqueous lining material composition excellent in corrosion resistance and adhesion to concrete.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a (co) polymer (A) having a total of at least two carboxyl groups and hydroxyl groups, and a crosslinking agent (B) having at least two functional groups capable of reacting with the (A). And an aqueous lining material composition containing the filler (C) and water.

The aqueous lining material composition (X) of the present invention has the following effects.
(1) Excellent corrosion resistance.
(2) Excellent adhesion to concrete.
(3) No amine is used.

<(Co) polymer (A)>
The (co) polymer (A) in the present invention has a total of at least two carboxyl groups and hydroxyl groups.
The (A) is preferably composed of an unsaturated monomer (a1) having a carboxyl group and / or an unsaturated monomer (a2) having a hydroxyl group as a constituent monomer from the viewpoint of adhesion to concrete and corrosion resistance. More preferably, (a1) and / or (a2) and an unsaturated monomer (a3) other than (a1) and (a2) are used as constituent monomers.

Unsaturated monomer (a1) having a carboxyl group:
Examples of (a1) include (poly) carboxylic acid (anhydride) having 3 to 30 carbon atoms (hereinafter sometimes abbreviated as C) having one polymerizable unsaturated group. In the present invention, the unsaturated (poly) carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic anhydride.
Among the (a1), as the unsaturated monocarboxylic acid, aliphatic (C3-24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic ring-containing (C6-24, For example, cyclohexene carboxylic acid); unsaturated poly (2-3 or more) carboxylic acid (anhydride) include unsaturated dicarboxylic acid (anhydride) [aliphatic dicarboxylic acid (anhydride) (C4-24, eg malee Acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof), alicyclic dicarboxylic acid (anhydride) (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid) Acid, methyltetrahydrophthalic acid, and anhydrides thereof)] and the like. (A1) may be used alone or in combination of two or more.
Of the above (a1), acrylic acid, methacrylic acid, maleic acid, maleic anhydride are preferred from the viewpoint of polymerizability and adhesiveness, and more preferred are acrylic acid, methacrylic acid, and a combination of acrylic acid and methacrylic acid. Particularly preferred is acrylic acid.

Unsaturated monomer having a hydroxyl group (a2):
Examples of (a2) include hydroxyalkyl (C1-5) (meth) acrylate.
Of the above (a2), preferred is hydroxyethyl (meth) acrylate.

Unsaturated monomers (a3) other than (a1) and (a2):
Examples of (a3) include styrene, alkyl (alkyl group having 1 to 4 carbon atoms) styrene, alkyl (alkyl group having 1 to 12 carbon atoms) (meth) acrylate [methyl (meth) acrylate, (meth) acrylic. Ethyl acid, (iso) butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, etc.], (meth) acrylamide Can be mentioned.
Of the above (a3), styrene, alkyl (alkyl group having 1 to 12 carbon atoms) (meth) acrylate is preferred from the viewpoints of polymerizability with (a1) and (a2), corrosion resistance, and adhesive adhesiveness. , A combination of them.

  The weight ratio [{(a1) + (a2)} / (a3)] of the monomers constituting (A) is preferably 3/97 to 60/40, more preferably 5 from the viewpoint of corrosion resistance and adhesiveness. / 95 to 50/50, particularly preferably 10/90 to 40/60.

The (co) polymer (A) can be produced by a known polymerization method, and from the viewpoint of productivity, preferred are an emulsion polymerization method and a solution polymerization method containing water.
Examples of the (co) polymer (A) that can be obtained by the above production method include (A) aqueous dispersion (A00) and (A) aqueous medium solution (A0). From the viewpoint of adhesiveness and anticorrosion, the aqueous dispersion (A00) of (A) is preferred.

Here, the aqueous dispersion refers to a dispersion of the particles (A) in an aqueous medium, and includes an emulsion.
The aqueous medium includes water and a mixture of water containing water as a main component (50% by weight or more) and an organic solvent described later. As the aqueous medium, water is preferred.

When (A) is the dispersion (A00), the volume average particle diameter of the (A) particles (unit: μm; only numerical values are shown below) is the handling of the lining material (X) described later, From the viewpoint of adhesiveness, it is preferably 0.01 to 3.0, more preferably 0.05 to 2.0, and particularly preferably 0.1 to 1.0.
The volume average particle diameter in the examples is a value measured using a laser diffraction / scattering particle size distribution measuring apparatus [trade name “LA-700”, manufactured by Horiba, Ltd.] applying light scattering theory. Yes (unit: μm).

  Examples of the organic solvent include aqueous solvents (water solubility at 25 ° C. of 10 g / 100 g water), such as ketones (acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), diethyl ketone, etc.), alcohols (methanol, ethanol, isopropanol). Etc.), and acetone, MEK, and isopropanol are preferable from the viewpoint of productivity. One or more organic solvents can be used.

  In (A00) and (A0), the content (% by weight) of (A) is preferably 20 to 80%, more preferably from the viewpoint of productivity and handling properties at the time of production of the lining material composition in the subsequent step. Is 30 to 70%, particularly preferably 40 to 60%.

The total content of carboxyl groups and hydroxyl groups in (A) [hereinafter sometimes abbreviated as the sum of carboxyl groups and hydroxyl groups in (A)] is based on the weight of (A), and has adhesion and anticorrosive properties. From this point of view, it is preferably 0.1 to 0.6 mol / kg, more preferably 0.2 to 0.5 mol / kg.
The glass transition temperature (sometimes abbreviated as Tg) of (A) is preferably −30 to 10 ° C., more preferably −20 to 5 ° C., from the viewpoints of the adhesiveness and anticorrosive properties of (X). is there.
In the present invention, the glass transition temperature is measured in accordance with a DSC (scanning differential thermal analysis) method (JIS K7121, “9.3 Determination Method of Glass Transition Temperature” of “Plastic Transition Temperature Measurement Method”). .
The total of the carboxyl group and hydroxyl group in (A) above, and the glass transition temperature in (A) are appropriately adjusted depending on the selection of the types (a1), (a2), and (a3) and their weights. Is possible.

  Weight average molecular weight of (A) [hereinafter abbreviated as Mw. The measurement is based on a gel permeation chromatography (GPC) method described later. ] Is preferably 5,000 to 600,000, more preferably 10,000 to 500,000, and particularly preferably 20,000 to 400,000 from the viewpoint of the balance between adhesiveness and anticorrosion.

The GPC measurement conditions for Mw and number average molecular weight (Mn) in the present invention are as follows.
<GPC measurement conditions>
[1] Apparatus: Gel permeation chromatography
[Model number “HLC-8120GPC”, manufactured by Tosoh Corporation]
[2] Column: “TSKgelG6000PWxl”, “TSKgel”
G3000PWxl "[both manufactured by Tosoh Corporation] are connected in series.
[3] Eluent: Methanol / water = 30/70 (volume ratio)
A solution in which 0.5% by weight of sodium acetate is dissolved.
[4] Reference material: polyethylene glycol (hereinafter abbreviated as PEG)
[5] Injection conditions: sample concentration 0.25% by weight, column temperature 40 ° C.

<Crosslinking agent (B) having at least two functional groups capable of reacting with (A)>
Examples of the crosslinking agent (B) in the present invention include polycarbodiimide (B1), polyisocyanate (B2), and mixtures thereof. Of the functional groups possessed by (B), preferred are a carbodiimide group and an isocyanate group.
The functional group of (B) is preferably 0.5 to 6.0 mol / kg, more preferably 1.0 to 5.0 mol / kg, from the viewpoint of reactivity with (A). It is.

  Examples of the crosslinking agent (B) include (B) itself, an aqueous dispersion (B00) of (B), and an aqueous medium solution (B0) of (B).

<Filler (C)>
Examples of the filler (C) in the present invention include an organic filler (C1), an inorganic filler (C2), and a mixture thereof.
Examples of the organic filler (C1) include polyolefin and polystyrene.
Examples of the inorganic filler (C2) include silicates [talc, clay, mica, glass, etc.] and inorganic oxides [titanium oxide, alumina, silica, etc.].
Of the above (C), preferred are a polystyrene filler and a glass filler from the viewpoint of anticorrosion and adhesiveness.

  Moreover, the volume average particle diameter of the above (C) is preferably 2 to 50 μm, more preferably 4 to 30 μm, from the viewpoints of adhesiveness, corrosion resistance, and workability.

<Water-based lining material composition (X)>
The aqueous lining material composition (X) of the present invention comprises the (co) polymer (A), a crosslinking agent (B) having at least two functional groups capable of reacting with the (A), a filler ( C) and water. The (X) is suitably used for various lining material applications, water and sewage lining material applications, particularly for lining materials for coating concrete structures.

The content based on the total weight of the (A), (B) and (C) is preferably 25 to 60% by weight (A) and 1 (B) from the viewpoints of adhesiveness, corrosion resistance and handling. 10 to 10% by weight, (C) is 35 to 70% by weight, more preferably (A) is 30 to 50% by weight, (B) is 3 to 7% by weight, and (C) is 45 to 65% by weight. is there.
The total weight of (A), (B) and (C) based on the weight of the lining material composition (X) is preferably 40 to 80% by weight, more preferably 45, from the same viewpoint as described above. ~ 60% by weight.

  The equivalent ratio of (A) and (B) [total of carboxyl group and hydroxyl group / functional group capable of reacting with (A) of (B)] is preferable from the viewpoints of adhesiveness and anticorrosion of the cured product. Is 0.4 to 2.5, more preferably 0.6 to 2.0, and particularly preferably 0.8 to 1.6.

The lining material composition (X) of the present invention is produced, for example, by the following methods (1) and (2).
(1) (A) to (C), and if necessary, immediately before using the later-described additive (D), the mixture is mixed to obtain a composition.
(2) Two liquids [A liquid containing (A) and B liquid containing (B)] are separately manufactured and mixed at the time of use to obtain a composition. (C) may be mixed with the liquid A and / or the liquid B in advance or at the time of use, but is preferably mixed with the liquid A and / or the liquid B in advance from an industrial viewpoint.
Of these composition forms, the form (2) is preferred from the industrial viewpoint.

  In both cases (1) and (2), the reaction proceeds after mixing (A) and (B). The pot life of the lining material composition (X) is preferably 30 to 360 minutes, more preferably 60 to 180 minutes.

  Examples of the mixing method of (A) to (C) and (D) contained if necessary in the present invention include a method using a mixer such as a universal mixer and a method using a mixer.

<Additive (D)>
The lining material composition (X) of the present invention may contain an additive (D) other than the above (A), (B), and (C) as necessary, as long as the effects of the present invention are not impaired. Good.
Examples of the additive (D) include curing accelerators, adhesion improvers, viscosity modifiers, antioxidants, stabilizers, plasticizers, waxes, pigments, dyes, antistatic agents, antibacterial agents, fungicides, and fragrances. , Flame retardants, dispersants, antifoaming agents, film forming aids, wetting agents and the like. In addition, (D) may be used alone or in combination of two or more.
The total addition amount of (D) is preferably 0.5 to 5% by weight based on the weight of the composition (X) after the addition.

<Concrete articles>
The concrete article of the present invention is a concrete article coated with a cured product of the aqueous lining material composition (X). That is, the concrete article can be obtained by applying a lining material composition and curing a concrete structure (such as a water and sewage pipe, a water treatment tank, and a water storage tank) for use in water and sewage.

The curing condition is preferably −10 to 35 ° C., and preferably 1 day to 7 days (including curing time).
The thickness of the cured product is preferably 50 μm to 3 mm, and more preferably 100 μm to 1 mm.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.

[Production of (co) polymer (A)]
<Production Example 1>
In a reaction vessel, 8.0 parts of acrylic acid, 7.0 parts of 2-hydroxyethyl methacrylate, 275.0 parts of 2-ethylhexyl acrylate, 6.0 parts of isobutyl methacrylate, 194.5 parts of styrene, polyoxyethylene-1 9.5 parts of ammonium (allyloxymethyl) alkyl ether and 162.0 parts of ion-exchanged water were charged and stirred to prepare an emulsion (a-1) of a monomer mixture.
In a separate reaction vessel, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium 1.0 part, ammonium peroxodisulfate 0.9 part, sodium thiosulfate pentahydrate 0.2 part, ion-exchanged water 335.9 Parts were charged and stirred to prepare an initiator / chain transfer agent solution (b-1).
The temperature of the initiator / chain transfer agent solution (b-1) was adjusted to 70 ° C., and the emulsion (a-1) of the monomer mixture was added dropwise over 3 hours with stirring. Further, by aging for 3 hours, 1000 parts of an aqueous dispersion (A00-1) of the (co) polymer (A-1) [content of (A-1): 50% by weight, volume average particle size: 0.00]. 20 μm] was obtained.
In addition, Tg of (A-1) is −20 ° C., weight average molecular weight (Mw) is 350,000, carboxyl group is 0.22 mol / kg, hydroxyl group is 0.11 mol / kg [total 0.33 mol / kg ]Met.

<Production Example 2>
In a reaction vessel, 15.0 parts of methacrylic acid, 250.0 parts of 2-ethylhexyl acrylate, 225.5 parts of styrene, 9.5 parts of polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, 162. 0 parts was charged and stirred to prepare an emulsion (a-2) of a monomer mixture.
In a separate reaction vessel, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium 1.0 part, ammonium peroxodisulfate 0.9 part, sodium thiosulfate pentahydrate 0.2 part, ion-exchanged water 335.9 Parts were charged and stirred to prepare an initiator / chain transfer agent solution (b-2).
The temperature of the initiator / chain transfer agent solution (b-2) was adjusted to 70 ° C., and the emulsion (a-2) of the monomer mixture was added dropwise over 3 hours with stirring. By further aging for 3 hours, 1000 parts of aqueous dispersion (A00-2) of (co) polymer (A-2) [content of (A-2): 50% by weight, volume average particle size 0.10 μm ] Was obtained.
The Tg of (A-2) was −10 ° C., the weight average molecular weight (Mw) was 370,000, and the carboxyl group was 0.35 mol / kg.

<Production Example 3>
In a reaction vessel, 22.0 parts 2-hydroxyethyl acrylate, 156.0 parts 2-ethylhexyl acrylate, 214.4 parts styrene, 7.6 parts polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, ion 262.0 parts of exchange water was charged and stirred to prepare an emulsion (a-3) of a monomer mixture.
In a separate reaction vessel, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium 1.0 part, ammonium peroxodisulfate 0.9 part, sodium thiosulfate pentahydrate 0.2 part, ion-exchanged water 335.9 Parts were prepared and stirred to prepare an initiator / chain transfer agent solution (b-3).
The temperature of the initiator / chain transfer agent solution (b-3) was adjusted to 70 ° C., and the emulsion (a-3) of the monomer mixture was added dropwise over 3 hours with stirring. By further aging for 3 hours, 1000 parts of the aqueous dispersion (A00-3) of the (co) polymer (A-3) [content of (A-3): 40% by weight, volume average particle size: 0.00]. 35 μm] was obtained.
The Tg of (A-3) was 0 ° C., the weight average molecular weight (Mw) was 300,000, and the hydroxyl group was 0.42 mol / kg.

<Examples 1 to 5, Comparative Example 1>
Each component was blended at 5 ° C. in accordance with the blending amount (part) in Table 1 and mixed with a glass rod (stirring time 5 minutes) to obtain each aqueous lining material composition.
Each aqueous lining material composition obtained was subjected to performance evaluation according to the following test methods (1) to (3). The evaluation results are shown in Table 1.

<Test method>
(1) Corrosion resistance [acid resistance]
The aqueous lining material composition (X) was poured onto a release film placed on a smooth surface so as to be 10 g (solid content) per 100 cm ² . A test specimen was obtained by curing for 7 days in an environment of temperature 5 ° C. and humidity 90% RH. The obtained specimen was immersed in a 1.1 mol / kg sulfuric acid aqueous solution while maintaining 40 ° C., and changes in the appearance of the specimen (swelling, wrinkle, softening, cracking, whitening) were observed. The number of days from the immersion date was evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: No change in appearance after 30 days ○: 20-29 days △: 10-19 days ×: 9 days or less

(2) Corrosion resistance [alkali resistance]
The alkali resistance test was carried out in the same manner as in the above (1) except that a saturated aqueous solution of calcium hydroxide was used in place of the 1.1 mol / kg sulfuric acid aqueous solution in the test method of (1) above. Then, the number of days from the dipping date at the time when the appearance change (blowing, wrinkle, softening, cracking, whitening) of the specimen was observed was evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: No change in appearance after 30 days ○: 20-29 days △: 10-19 days ×: 9 days or less

(3) Adhesiveness [Adhesive strength] (Unit: N / mm ² )
1.6 g of the aqueous lining material composition (X) is placed on the smooth surface (1600 mm ² ) of the upper tensile steel jig of the Kenken tensile tester [Oxjack Co., Ltd.] to smooth the mortar plate An upper tensile steel jig was placed on the polished surface so as to contact the aqueous lining material composition (X). It was cured for 7 days under a temperature of 5 ° C. and a humidity of 90% RH, and the adhesive strength was measured with a Kenken tensile tester.

Each abbreviation in the table is as follows.
<Crosslinking agent (B)>
B0-1: Polycarbodiimide [Brand name “Carbodilite V-10”, manufactured by Nisshinbo Chemical Co., Ltd.,
40% active ingredient, carbodiimide group concentration of (B): 2.44 mol / kg]
B-2: Polyisocyanate [Brand name “Duranate WT30-100”, manufactured by Asahi Kasei Chemicals Corporation,
Active ingredient amount 100%, isocyanate group concentration 3.93 mol / kg]

<Filler (C)>
C-1: Polystyrene filler [trade name “SBX-8”, manufactured by Sekisui Plastics Co., Ltd.,
Volume average particle diameter 8μm]
C-2: Glass filler [Product name: “Glass flake RCF-015”, manufactured by Nippon Sheet Glass Co., Ltd.,
Volume average particle diameter 15 μm]

  From the results of Table 1, it can be seen that the aqueous lining material composition of the present invention is superior in corrosion resistance (acid resistance, alkali resistance) and adhesion to concrete without using an amine as compared with the comparative one.

The aqueous lining material composition of the present invention does not use an amine and imparts excellent corrosion resistance and adhesion to concrete to the cured product.
For this reason, it can be suitably used as a lining material for various lining material applications, water and sewage systems and related lining material applications, particularly for coating concrete structures, and is extremely useful.

Claims (10)

  A (co) polymer (A) having a total of at least two carboxyl groups and hydroxyl groups, a crosslinking agent (B) having at least two functional groups capable of reacting with the (A), and a filler (C And an aqueous lining material composition (X) comprising water.   The (co) polymer (A) comprises an unsaturated monomer (a1) having a carboxyl group and / or an unsaturated monomer (a2) having a hydroxyl group, and an unsaturated monomer (a3) other than (a1) and (a2) ) As a constituent monomer.   (A1) is (meth) acrylic acid, (a2) is hydroxyalkyl (alkyl group having 2 to 4 carbon atoms) (meth) acrylate, and (a3) is styrene and / or alkyl (alkyl group). The aqueous lining material composition according to claim 2, which is a (meth) acrylate having 1 to 12 carbon atoms.   The total content of the carboxyl group and the hydroxyl group of the (co) polymer (A) is 0.1 to 0.6 mol / kg based on the weight of (A). An aqueous lining material composition.   5. The aqueous lining material composition according to claim 1, wherein the (co) polymer (A) has a volume average particle diameter of 0.01 to 3.0 μm.   The aqueous lining material composition according to any one of claims 1 to 5, wherein the crosslinking agent (B) is at least one selected from the group consisting of polycarbodiimide (B1) and polyisocyanate (B2).   The aqueous lining material composition according to any one of claims 1 to 6, wherein the filler (C) is at least one selected from the group consisting of a polystyrene filler and a glass filler.    The content based on the total weight of (A), (B) and (C) is 25 to 60% by weight of (A), 1 to 10% by weight of (B), and 35 to 70% by weight of (C). The aqueous lining material composition according to any one of claims 1 to 7.   The aqueous lining material composition according to any one of claims 1 to 8, wherein the total weight of (A), (B) and (C) based on the weight of the lining material composition is 40 to 80% by weight.   A concrete article coated with a cured product of the aqueous lining material composition (X) according to any one of claims 1 to 9.