JP2716798B2 - Elastic color pavement composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resilient color paving material composition, and particularly to a tennis court, an athletic court and the like formed by coating the surface of asphalt, concrete or the like. The present invention relates to an aqueous elastic color pavement composition having suitable elasticity.

[Conventional technology and its problems]

The present inventor has previously proposed an aqueous color paving material using an acrylic aqueous emulsion having a multilayer structure (Japanese Patent Application Laid-Open (JP-A) No. 63-155681).

This pavement material was excellent in adhesiveness to asphalt and other base materials, water resistance, blister resistance, abrasion resistance, etc., but it has a moderate elasticity especially required for tennis courts and athletic courts. Was not fully satisfactory.

[Object of the invention]

The present invention is an improvement of the aqueous color pavement described in the above-mentioned JP-A-63-156871, and has a moderate elasticity and smoothness sufficiently satisfying for sports facilities, and a moderate frictional resistance between athletic shoes. It is an object of the present invention to provide an aqueous color paving material composition having:

[Means for solving the problem]

The present inventor has conducted intensive studies to solve the above problems, and as a result, found that an elastic color pavement composition containing a rubber powder having a specific particle size distribution can achieve the object of the present invention, and completed the present invention. Reached.

That is, the present invention relates to (a) three or more monomers including an acrylic crosslinking reactive monomer, and a polymer having a glass transition point of 20 or more.
In the presence of a polymer emulsion obtained by emulsion polymerization of the monomer (I) having a temperature of not more than 3 ° C., three or more kinds of monomers including an acrylic crosslinking reactive monomer, and the glass transition point of those polymers is not less than 40 ° C. 100 parts by weight of acrylic polymer emulsion obtained by emulsion polymerization of monomer (II) (b) Maximum diameter is larger than 1.2 mm 0 to 10% by weight 1.2 to 0.3 mm 30 to 80% by weight From 0.3 mm Rubber powder composed of 20 to 70% by weight 50 to 400 parts by weight (c) Film forming aid 1 to 30 parts by weight (d) Color pigment 2 to 60 parts by weight (e) Aggregate 5 to 100 parts by weight and (F) A water-based resilient color pavement composition comprising 0.3 to 30 parts by weight of a dispersant.

The acrylic polymer emulsion (a) of the present invention is generally referred to as a multilayer emulsion, and is a known emulsion polymerizing the monomer (II) in the presence of a polymer emulsion obtained by emulsion polymerization of the monomer (I). It is synthesized by a multi-stage polymerization method.

Examples of the acrylic crosslinking reactive monomer used as one of the monomer (I) and the monomer (II) constituting the emulsion (a) include acrylamide, N-methylolacrylamide, glycidyl methacrylate, and glycidyl acrylate. These monomers are used in an amount of 0.5 to 15% by weight based on the total amount of the monomers (I) and (II). The amount of these monomers used is 0.
If it is less than 5% by weight, the water resistance is poor, and if it is more than 15% by weight, the film is too hard, which is not preferable.

The monomer (I) contains at least one of the above-mentioned acrylic cross-linking reactive monomers, and has a glass transition point of 20 ° C. by combining two or more other monomers.
The following polymer is constituted. Here, other monomers include acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. And methacrylic acid esters such as acrylic acid and methacrylic acid; and compounds such as styrene, vinyl acetate, chloroprene, ethylene, butadiene, acrylonitrile, and veoba.

Of these monomers, unsaturated carboxylic acids are added in an amount of 0.2 to 8
It is preferred to use it by weight. The unsaturated carboxylic acid promotes the crosslinking of the acrylic crosslinking reactive monomer and acts to increase the stability of the emulsion.

As a method of combining monomers that make the glass transition point of the polymer 20 ° C. or lower, it is preferable to combine two or more monomers having a glass transition point of the homopolymer of 70 ° C. or higher and a monomer of 0 ° C. or lower. Usually, a homopolymer having a glass transition point of 70 ° C. or higher is used in combination of 10 to 60% by weight, and a monomer having a glass transition point of 0 ° C. or lower is used in combination of 90 to 40% by weight. If the amount of the monomer having a glass transition point of the homopolymer of 70 ° C. or higher is less than 10% by weight, the water resistance is poor, and
If it is 60% by weight or more, the elasticity of the film is poor, which is not preferable.

The monomer (II) contains at least one of the above-mentioned acrylic cross-linking reactive monomers, and has a glass transition point of 40 ° C. by combining two or more other monomers.
The above polymer is constituted. Here, as the other monomer, the same monomer as the other monomer used to constitute the monomer (I) is used. In addition, as a method of combining monomers for setting the glass transition point to 40 ° C. or higher, it is also possible to combine two or more monomers having a glass transition point of a homopolymer of 70 ° C. or higher and a monomer of 0 ° C. or lower. preferable. Usually, a homopolymer having a glass transition point of 70 ° C. or more is used in combination of 60 to 100% by weight, and a monomer having a glass transition point of 0 ° C. or less is used in combination of 40 to 0% by weight. If the amount of the monomer having a glass transition point of the homopolymer of 70 ° C. or higher is less than 60% by weight, the blister resistance and the adhesiveness are inferior.

Examples of the above-mentioned monomer whose homopolymer has a glass transition point of 70 ° C. or higher include acrylonitrile, methyl methacrylate, t-butyl methacrylate, and styrene. Further, the glass transition point of the homopolymer is 0 ° C.
Examples of the following monomers include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and the like.

The glass transition point of the copolymer is determined by actual measurement,
It can also be estimated by the following formula according to the combination of monomers.

1 / Tg = Wa / Tga + Wb / Tgb + ... Tg; glass transition point of copolymer (゜ K) Tga; glass transition point of homopolymer of a monomer (゜ K) Tgb; glass transition of homopolymer of b monomer Point (ΔK) Wa; a weight fraction of monomer Wb; b weight fraction of monomer In the present invention, the ratio of the amount of the monomer (I) to the amount of the monomer (II) is usually (I) / (II) = 40 / It is in the range of 60 to 90/10.

The rubber powder (b) used in the present invention may be in a spherical, fibrous, cubic, or other form, and the shape is not particularly limited, but it is necessary that the maximum particle size has the following particle size distribution. . That is, rubber powder composed of 0 to 10% by weight larger than 1.2 mm, 30 to 80% by weight of 1.2 to 0.3 mm, and 20 to 70% by weight smaller than 0.3 mm is used.

If the content of the rubber powder having a particle diameter of less than 0.3 mm exceeds 70% by weight, the smoothness of the surface is good, but the elasticity is insufficient, and the content of the rubber powder having a particle diameter of more than 1.2 mm is 10%. If the content is more than 10% by weight, the surface is inferior in smoothness and is not suitable for use in tennis courts and the like.

As the rubber powder (b) used in the present invention, any rubber powder such as urethane-based, SBR-based, and natural rubber-based can be used, and is not particularly limited. Recycled rubber from production waste can also be used for economic reasons.
The color of the rubber powder (b) is white, green, black,
Since there is no particular restriction such as red, a desired color can be selected.

The amount of the rubber powder (b) is 50 parts by weight based on 100 parts by weight of the solid content of the acrylic polymer emulsion (a).
It is necessary to mix up to 400 parts by weight.If the amount of rubber powder is less than 50 parts by weight, the elasticity of the formed coating film is insufficient, and if it exceeds 400 parts by weight, the surface becomes rough. It is not preferable because rubber powder is scattered or scattered.

As the film-forming auxiliary (c) used in the present invention, known materials can be used, and examples thereof include substances such as phthalic acid-based plasticizers, texanol-based, cellosolve-based solvents, butyl acetate, xylene, and toluene. The role of the film-forming aid (c) is to impart film-forming properties of the color paving material composition at room temperature.

It is necessary to add the film-forming auxiliary (c) in an amount of 1 to 30 parts by weight based on 100 parts by weight of the solid content of the acrylic polymer emulsion (a). If the amount is less than 30 parts by weight, the adhesion to the object to be coated will be poor, and if it exceeds 30 parts by weight, the formed film will have poor blister resistance, which is not preferable.

Examples of the coloring pigment (d) used in the present invention include inorganic pigments such as titanium oxide-based pigments, bengara pigment-based pigments, and chromium oxide-based pigments, and organic pigments such as phthalocyanine-based pigments and azo-based pigments. The amount of the color pigment to be added must be 2 to 60 parts by weight based on 100 parts by weight of the solid content of the acrylic polymer emulsion (a). If it is sufficient, and if it exceeds 60 parts by weight, the degree of coloring will be too strong, giving the eyes a feeling of fatigue.

Examples of the aggregate (e) used in the present invention include silica sand,
Examples include silica stone powder, asbestin, zinc white, cold water stone, mica powder, talc, clay, aluminum hydroxide, diatomaceous earth, gypsum, barium carbonate, barium sulfate, glass powder, calcium metasilicate powder, and the like. The role of the aggregate (e) is to reduce shrinkage when the coating film dries.

It is necessary to add these aggregates (e) in the range of 5 to 100 parts by weight based on 100 parts by weight of the solid content of the acrylic polymer emulsion (a). If the amount of the aggregate is less than 5 parts by weight, the coating film shrinks greatly upon drying and cracks are likely to occur, and if it exceeds 100 parts by weight, the elasticity becomes insufficient, which is not preferable. In addition, diatomaceous earth is 5-50
When used in parts by weight, a good matte color paving material composition can be obtained.

Examples of the dispersant (f) used in the present invention include sodium polyacrylate, sodium tripolyphosphate, styrene-maleic resin, anionic or nonionic surfactant, and the like. The dispersant (f) acts as an auxiliary for dispersing the rubber powder (b), the coloring pigment (d), and the aggregate (e).

The dispersant (f) is an acrylic polymer emulsion (a)
It is necessary to add 0.3 to 30 parts by weight based on 100 parts by weight of the solid content. If the amount of the dispersant (f) is less than 0.3 parts by weight, the dispersion stability of the color pavement composition is poor, and if it is more than 30 parts by weight, the water resistance is undesirably reduced.

The elastic color pavement composition of the present invention contains the above (a) to
In addition to the component (f), a thixotropic agent is preferably added to further stabilize the composition.

Examples of the thixotropic agent include synthetic finely divided silica, bentonite, organic bentonite, and ultrafine surface-treated calcium carbonate. The thixotropy-imparting agent acts as an auxiliary for preventing separation of the rubber powder (b) and the aggregate (e).

The thixotropic agent is added in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the solid content of the acrylic polymer emulsion (a). If the amount of the thixotropy-imparting agent is less than 0.1 part by weight, the stability and separation / sedimentation stability of the color pavement composition will be poor.

Other components that are optionally added to the elastic color pavement composition of the present invention include a general paint additive,
For example, antifoaming agents, wetting agents, thickening agents, neutralizing agents, preservatives, antifreezing agents and the like can be mentioned. The order of adding these various compounding materials is not particularly limited.

Since the elastic color pavement composition of the present invention is of a room temperature drying type, no heating operation or the like is required at all, and a normal coating method, for example, a spray, a rake, a trowel,
For example, it can be directly painted on the surface of asphalt concrete, concrete, mortar and the like.

Examples of places to be constructed using the elastic color pavement composition of the present invention include simple roads, tennis courts, promenades, indoor and outdoor poolsides, sports grounds, cycling roads, and rooftops of buildings.

Next, the condition of the base when the elastic color pavement composition of the present invention is coated on the base will be described.

In the normal case, the intended purpose can be sufficiently achieved only by directly coating the surface of the base material such as asphalt or concrete with the elastic color pavement composition. In the case where the surface roughness is increased and a smooth finished surface is required, it is preferable to apply an undercoat paving material between the base surface and the elastic color paving material layer. As the undercoating pavement material, for example, a mixture obtained by adding water to a mixture of an acrylic polymer emulsion, a film forming aid, a coloring pigment, silica sand, and the like, followed by stirring and mixing, and applying this by spraying or rake. It is possible. In addition, an undercoat pavement material such as an asphalt emulsion type and a cement type can be used.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

 In the examples, parts and% are based on weight.

Synthesis Example <Synthesis of acrylic polymer emulsion> 26 parts of water were charged into a polymerization vessel, and 20 parts of water, 1 part of polyoxyethylene nonylphenyl ether, 3 parts of polyoxyethylene lauryl sulfate, 9 parts of styrene, and 9 parts of acrylic acid Emulsification at 85 ° C. for 3 hours while sequentially adding an emulsion obtained by mixing 21 parts of butyl, 1 part of glycidyl methacrylate, 0.2 part of acrylamide and 0.2 part of methacrylic acid, and an aqueous catalyst solution obtained by dissolving 0.2 part of potassium persulfate in 4 parts of water. Polymerization was carried out to form an emulsion of a polymer to be a central layer [polymer emulsion of monomer (I)]. The glass transition point Tg of this polymer was −20 ° C.

Next, the polymer emulsion was heated to 90 ° C., and 11 parts of styrene, 1 part of glycidyl methacrylate, and 0.7 part of methacrylic acid were mixed with the monomer emulsion to have a glass transition point Tg of 98 ° C. [monomer (II)] Was continuously added for 2 hours, and the solid content was about 46%, the viscosity was about 200 cps, and the pH was 9.0.
Was obtained.

Examples 1 to 3 Texanol 9 was used as a film-forming auxiliary with respect to 100 parts in terms of solid content of the acrylic emulsion obtained in the above synthesis example.
Parts, 100 parts of rubber powder having various particle size distributions shown in Table 1,
30 parts of iron oxide-based red iron oxide as a coloring pigment, 50 parts of silica powder as an aggregate, 3 parts of sodium polyacrylate as a dispersant, 1.5 parts of organic bentonite, 0.3 parts of hydroxyethylcellulose, and 0.7 parts of an antifoaming agent as a thixotropic agent Then, the mixture was sufficiently dispersed and mixed to obtain an elastic color pavement composition of the present invention.

Example 4 Based on 100 parts in terms of solid content of the acrylic emulsion obtained in the above synthesis example, butyl cellosolve 1 was used as a film-forming aid.
0 parts, 200 parts of rubber powder having various particle size distributions shown in Table 1,
30 parts of iron oxide based red iron oxide as color pigment, 50 parts of silica powder as aggregate, 3 parts of sodium polyacrylate and 2 parts of sodium tripolyphosphate as dispersants, hydroxyethyl cellulose
0.2 parts and 0.7 parts of an antifoaming material were added and sufficiently dispersed and mixed to obtain an elastic color pavement composition of the present invention.

Comparative Example 1 A color pavement material composition was obtained in the same manner as in Example except that no rubber powder was added.

Comparative Examples 2 and 3 A color pavement composition was obtained in the same manner as in Example except that rubber powder having a particle size distribution shown in Table 1 was used.

Note that the rubber powder used in the above Examples and Comparative Examples was produced by reusing production waste.

(1) water resistance, (2) adhesive strength, (3) abrasion resistance of the color pavement composition obtained in the above Examples and Comparative Examples,
(4) Weather resistance, (5) blister resistance, (6) smoothness and (7) elasticity were evaluated by the following methods, and the results are shown in Table-2.

(1) Water resistance Each color paving material composition is applied to asphalt roofing paper by spraying to a thickness of about 1 mm, allowed to dry at room temperature for 7 days, naturally dried, immersed in water for 48 hours, and visually inspected for their surface condition Was observed, and the presence or absence of abnormality was determined based on the following criteria.

Evaluation criteria ○: No abnormality △: Less whitening and swelling ×: Significant whitening and swelling (2) Adhesive strength Normal condition: Spray each color paving material composition on asphalt board (30cm × 30cm × 5cm) to a thickness of about 1mm , And allowed to stand at room temperature for 7 days, and after natural drying, the tensile strength was measured with a Kenken-type adhesion tester.

Water resistance: Each color pavement material is coated on asphalt board (30cm × 30cm × 5cm) under the same conditions as the normal adhesive strength described above, left at room temperature for 7 days, air-dried, and left in water for 2 days. Tensile strength was measured with an adhesion tester.

(3) Abrasion resistance Normal condition: Each color paving material composition is sprayed on a round slate plate with a diameter of about 10cm to a thickness of about 1mm, left at room temperature for 7 days, air-dried, and a Taber abrasion test The number of wear mg per 100 rotations was measured with a machine. (According to JIS K5665) Water resistance: Each color paving material is applied to a slate plate under the same conditions as the normal wear resistance described above, left at room temperature for 7 days, air-dried, left in water for 1 day, and then a Taber abrasion The number of wear mg per 100 rotations was measured with a test machine. (Based on JIS K5665) (4) Weather resistance (based on JIS K5400) Paint each color pavement composition to a thickness of about 1 mm by spraying on a slate plate (10 cm × 5 cm × 0.5 cm) and leave it at room temperature for 7 days. After air drying, an accelerated weathering test with a sunshine weather meter was performed for 600 hours, and the color pavement composition was observed and evaluated according to the following criteria.

Evaluation criteria △: Discoloration ○: No abnormality (5) Blister resistance Each color paving material composition was applied to an asphalt board (7 cm × 15 cm × 3 cm) by spraying at 600 g / m ² , dried and then repeatedly applied twice more. I do. This is left standing at room temperature for 7 days, naturally dried, immersed in water for 24 hours, and immediately after being taken out, the surface temperature is heated to 80 ° C. in 20 minutes by infrared irradiation and blisters generated on the color pavement (fukuro) Observe
Evaluation was made according to the following criteria.

Evaluation criteria ○: No abnormality △: Blister generation of less than 20% ×: Blister generation of 20% or more (6) Smoothness 600 g / m ² of each color pavement composition by spraying on asphalt board (30 cm × 30 cm × 5 cm) After the coating and drying, the coating is repeated once more. This was allowed to stand at room temperature for 2 days and air-dried, and then the smoothness (roughness) of the surface was evaluated by finger touch according to the following criteria.

Criteria ◎: roughness much less ○: roughness less △: roughness Some more ×: roughness often (7) elasticity asphalt plate (30 cm × 30 cm × 5 cm) each colored paving material composition by spraying to a 600 g / m ² coating After drying, the coating is repeated twice more. The golf ball was allowed to stand at room temperature for 7 days, allowed to dry naturally, and then dropped from a height of 1 m. The resilience of the golf ball and the hardness measured by a Shore hardness tester were used to determine the elasticity according to the following criteria.

Judgment criteria ◎: large elasticity ○: slightly large elasticity △: slightly small elasticity ×: small elasticity [Effect of the Invention] The elastic color pavement composition of the present invention maintains water resistance, adhesive strength, abrasion resistance, blister resistance and weather resistance as compared with conventional ones, and sports facilities such as tennis courts. It has both smoothness, elasticity and friction resistance that can be suitably used. For this reason, since it is possible to exercise with a soft touch, there is little fatigue even when exercising for a long time.
In addition, since the shoe has moderate friction with the athletic shoes, even if the user exercises intensely, it hardly slips and falls.

Claims (1)

(57) [Claims] (1) A polymer emulsion obtained by emulsion-polymerizing a monomer (I) which is at least three kinds of monomers including an acrylic crosslinking reactive monomer and whose polymer has a glass transition point of 20 ° C. or lower. Monomers (II), which are three or more monomers including acrylic cross-linking reactive monomers in the presence thereof, and whose polymers have a glass transition point of 40 ° C. or higher.
Polymer emulsion obtained by emulsion polymerization of
100 parts by weight (b) The maximum diameter is larger than 1.2 mm 0 to 10% by weight 1.2 to 0.3 mm 30 to 80% by weight Smaller than 0.3 mm 20 to 70% by weight Rubber powder consisting of 50 to 400 parts by weight (C) 1 to 30 parts by weight of a film-forming auxiliary (d) 2 to 60 parts by weight of a coloring pigment (e) 5 to 100 parts by weight of aggregate and (f) 0.3 to 30 parts by weight of a dispersant Water-based elastic color pavement composition.