JPS6329900B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color paving material that dries at room temperature and is composed mainly of an acrylic acid ester-based emulsion copolymer emulsion into which a crosslinking group has been introduced. This relates to colored paving materials made by mixing and dispersing aggregate, coloring pigments, and dispersants, and has better water resistance, abrasion resistance, adhesion, impact resistance, oil resistance, and Excellent performance such as weather resistance, especially water resistance,
The object of the present invention is to provide a colored paving material with significantly improved adhesive properties. Compositions conventionally used as binders for color paving materials that dry at room temperature, such as Japanese Patent Publication No. 55-33745
The composition using the acrylic acid ester copolymer emulsion introduced in the publication had problems in practical use because it was poor in water resistance, adhesiveness, etc. As a result of intensive research to solve these problems, the present inventors added a coating aid, an aggregate, a color pigment, and a dispersant to an acrylic acid ester emulsion copolymer emulsion into which an acrylic crosslinking group has been introduced. Water-based color paving materials that dry at room temperature and are mixed and dispersed are water resistant,
It has excellent abrasion resistance, adhesion, impact resistance, oil resistance, weather resistance, etc. In particular, it has extremely excellent adhesion and water resistance, and can be sufficiently applied for practical purposes. In other words, we discovered that the present invention is fully applicable to places with harsh conditions, such as playgrounds, cycling roads, shopping street roads, and building rooftops, which were conventionally considered difficult to use in water systems, and led us to complete the present invention. Ivy. The present invention will be explained in detail below. The color pavement material of the present invention comprises (1) 44 to 96% by weight of acrylic ester, (2) 0 to 55% by weight of methacrylic ester and/or styrene, (3) glycidyl methacrylate, N-methylolacrylamide, acrylamide, 0.1 to 5% by weight of one or more types selected from glycidyl acrylate, (4) 0.5 to 5% by weight of unsaturated carboxylic acid, and an emulsifier containing monomers of (1) to (4) above as constituent units. 100 parts by weight of polymer emulsion solid content, 1 to 20 parts by weight of membrane forming aid, 250 to 650 parts by weight of aggregate, 5 parts by weight of coloring pigment.
~30 parts by weight and 0.5 to 3 parts by weight of a dispersant. That is, the emulsion copolymer emulsion has the following (1) to
It is obtained by emulsion polymerization of the monomer (4) in the presence of a catalyst and an emulsifier. (1) Consists of acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., and the amount used is 44 to 96% by weight. If it is less than 44% by weight, the adhesion to the substrate (concrete, asphalt, asphalt concrete, solvent-based or water-based synthetic resin system, such as epoxy system, urethane system, acrylic system, etc.) will be poor, and 96% by weight. If it exceeds %, the workability when painting colored paving materials will be poor, which is not preferable. (2) Consists of methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. and/or styrene, in an amount of 0 to 55% by weight. If it exceeds 55% by weight, the colored paving material will be too hard and its adhesion to the substrate will be poor, which is not preferable. (3) It is composed of one or more selected from glycidyl methacrylate, N-methylolacrylamide, acrylamide, and glycidyl acrylate, and the amount used is 0.1 to 5% by weight, and it is necessary to have crosslinking properties. be. If it is less than 0.1% by weight, the water resistance, abrasion resistance, oil resistance, etc. when adhering to the base of the color paving material will be poor, and if it exceeds 5% by weight, the color paving material will be too hard and have poor adhesion to the base, so it is preferable. do not have. (4) Consists of unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, etc., and the amount used is 0.5 to 5% by weight, and if it is less than 0.5% by weight, the crosslinking monomer of (3) above is used. The crosslinking reactivity with the emulsion copolymer decreases, and it is difficult to obtain a stable emulsion copolymer emulsion. Moreover, if it exceeds 5% by weight, the water resistance of the colored pavement material when it is adhered to the base will be poor, which is not preferable. As a catalyst, potassium persulfate is used as a persulfate;
Examples of emulsifiers include ammonium persulfate, nonionic emulsifiers such as polyoxyethylene nonyl phenyl ether, and anionic emulsifiers such as alkyl allyl sulfates.
It is appropriate to use one or more types of catalytic emulsifiers, but the emulsifiers are not limited to those mentioned above. The film-forming agent is used to lower the film-forming temperature of the above-mentioned acrylic acid ester emulsion copolymer emulsion (hereinafter referred to as the emulsion) of the present invention to about 0°C or lower, and the amount used is the same as that of the emulsion solid. minutes
1 to 20 parts by weight is required per 100 parts by weight, and if it is less than 1 part by weight, the film-forming properties of the emulsion will be poor and the color paving material will not have sufficient adhesion to the base, so it is not preferable, and if it exceeds 20 parts by weight. This is not preferable because the viscosity increases significantly and fluidity is inhibited, resulting in poor workability and staining properties. Coating aids include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monosec-butyl ether, and ethylene glycol. Mono tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono sec-butyl ether, diethylene glycol mono tert-butyl ether, ethylene glycol monomethyl ether acetate , ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol monosec
-butyl ether acetate, ethylene glycol monotert-butyl ether acetate, diethylene glycol monomethyl ether acetate,
General formula R ₁ −( OC ₂ H ₄ O)
Alkylene glycol derivatives represented by n-R ₂ (wherein R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is H or COCH ₃ , and n is an integer of 1 or 2), acetoacetic acid 1 selected from the group consisting of methyl, ethyl astoacetate and isophorone
One or more species may be mentioned. Mention may be made of butyl acetate, xylene, toluene, phthalate esters such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, and the like. Examples of aggregates include silicic acid, asbestos, anhydrite, stone powder, fibers, calcium carbonate, and glass beads, and the amount used is 100% of the solid content of the emulsion.
250 to 650 parts by weight is required, and if outside this range, the color paving material will have poor abrasion resistance, adhesion,
It is not preferred because it has poor water resistance. Coloring pigments include, for example, titanium oxide, Bengara, ultramarine,
Examples include inorganic pigments such as chromium oxide, cadmium yellow, chrome yellow, lead white, and carbon black, and organic pigments such as azo, triphenylmethane, quinoline, anthraquinone, and phthalocyanine pigments. The amount used is 5 to 30 parts by weight per 100 parts by weight of the emulsion solid content,
If it is out of this range, the degree of coloration of the colored pavement material will not be appropriate and will have a negative effect on weather resistance. Dispersants are necessary to improve the dispersion stability of color paving materials, such as sodium polyacrylate, sodium tripolyphosphate, water-soluble polymer compounds, specifically CMC, Poval, MC, HEC, etc. I can list them. The amount used is 0.5 to 3 parts by weight based on 100 parts by weight of the solid content of the emulsion. If it is less than 0.5 parts by weight, the dispersion stability of the colored paving material will be poor, and if it exceeds 3 parts by weight, it will be difficult to adhere the colored paving material to the base. This is not preferable because water resistance decreases. Since the colored paving material of the present invention dries at room temperature, there is no need for any heating equipment, and it can be applied to the base material such as asphalt, concrete, etc. using normal painting methods such as spraying, rake, and troweling.
Can be applied directly to surfaces such as asphalt concrete and mortar. Specific construction locations include simple roads, tennis courts, promenades, indoor and outdoor pool sides, playgrounds, walking roads, and building rooftops. In particular, when applying the color paving material of the present invention once applied, for example, the emulsion (solid content approximately 30 to 70% by weight) with a film-forming agent added may be used as a primer as a base. May be used. In addition, for the purpose of preventing contamination of the surface coated with the color paving material of the present invention, acrylic esters such as methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid, etc. may be used as necessary. copolymer emulsions may be used as top coats. Additionally, antifoaming agents, thickeners, preservatives, and the like may be added as additives. An example of the synthesis of an acrylic acid ester emulsion copolymer emulsion into which an acrylic crosslinking group has been introduced for use in the present invention will be shown below. Note that parts and percentages are based on weight. Synthesis Example 1 Put 16 parts of water and 1.3 parts of polyoxyethylene nonyl phenyl ether into a polymerization can, add 12 parts of water,
Polyoxyethylene nonyl phenyl ether 3.4
parts, 25 parts of styrene, 21 parts of 2-ethylhexyl acrylate, 0.1 part of acrylamide, 0.3 parts of acrylic acid.
An aqueous catalyst solution prepared by dissolving 0.2 parts of ammonium persulfate in 3 parts of water, and further HEC
(Hydroxyethyl cellulose) 0.1 part dissolved in 5.6 parts of water to adjust the viscosity at approximately 80°C.
Emulsion polymerization was carried out for 3 hours and 30 minutes to obtain an emulsion copolymer emulsion with a solid content of about 50%, a viscosity of about 2000 cps, and a pH of 9.0. Synthesis Example 2 A polymerization can was charged with 38 parts of water and 0.3 parts of sodium alkyl sulfate, and mixed monomer liquid of 15 parts of ethyl acrylate, 15 parts of methyl methacrylate, 1.5 parts of methacrylic acid, and 0.9 parts of glycidyl methacrylate, and persulfuric acid. Emulsion polymerization is carried out at about 80 to 90°C for about 2 hours while sequentially adding a catalyst aqueous solution in which 0.1 part of potassium is dissolved in 0.5 parts of water, and a mixture of 3 parts of ethylene diglycol, 6 parts of isopropyl alcohol, and 5 parts of water and aqueous ammonia are added. Added 3 parts to make solid content 36%, viscosity 10,000 cps, PH
An emulsion copolymer emulsion of 8.5 was obtained. Example 1 Polyoxyethylene nonyl phenyl ether 5 was added to 100 parts of the solid content of the emulsion obtained in Synthesis Example 1.
, 311 parts of silica sand No. 7, 17 parts of asbestos W-4, 11 parts of chromium oxide type oxide green GN, 1 part of sodium tripolyphosphate, and 0.5 part of an antifoaming agent were added and thoroughly dispersed and mixed to obtain the colored paving material of the present invention. Ta. Example 2 100 parts of emulsion solid content obtained in Synthesis Example 2, 6 parts of diethylene glycol monobutyl ether acetate, 592 parts of silica sand No. 7, and 16 parts of asbestos W-35
1 part, 21 parts of iron oxide, 2 parts of sodium tripolyphosphate, and 1 part of an antifoaming agent were added and sufficiently dispersed and mixed to obtain a colored pavement material of the present invention. Example 3 100 parts of emulsion solid content obtained in Synthesis Example 1, 3 parts of Texanol, 3 parts of dibutyl phthalate, 200 parts of silica sand No. 7, 200 parts of silica sand No. 8, asbestos W-35
15 parts of iron oxide, 2 parts of sodium tripolyphosphate, and 1 part of an antifoaming agent were added and sufficiently dispersed and mixed to obtain a colored paving material of the present invention. Example 4 To 100 parts of the solid content of the emulsion obtained in Synthesis Example 2, 6 parts of Texanol, 200 parts of silica powder, 100 parts of silica sand No. 6,
100 parts of Silica Sand No. 7, 15 parts of Asbestos W-35, Chromium Oxide Green GN (manufactured by Bayer)
1.5 parts of sodium tripolyphosphate, 2 parts of sodium tripolyphosphate, and 1 part of an antifoaming agent were added and sufficiently dispersed and mixed to obtain a colored paving material of the present invention. Comparative Example 1 A color pavement material was obtained by dispersing and mixing an emulsion polymerized by emulsion polymerization in the same manner as in Example 1, except for the crosslinkable monomer acrylamide used in Synthesis Example 1. The physical property test results of the colored pavement materials obtained in the above Examples and Comparative Examples are shown in Table 1. From the results shown in Table 1, it is clear that the colored pavement material of the present invention is particularly superior in adhesive strength, workability, water resistance, oil resistance, abrasion resistance, and weather resistance compared to conventional colored pavement materials. It became. The physical property evaluations of these Examples and Comparative Examples are listed in Table 1, and the test methods and evaluation criteria for the physical property test items are shown below. (1) Water resistance Each color paving material was applied to asphalt-rubbing paper with a metal trowel to a thickness of approximately 1 mm, left to dry naturally at room temperature for 7 days, and then immersed in water for 48 hours to visually inspect the surface condition. Observation was made to determine the presence or absence of abnormalities. That is, no abnormalities; 〇, little whitening and swelling; △, significant whitening and swelling; The difficulty level of the painting work was observed and evaluated based on the following criteria. Good; 〇, Slightly poor; △, Poor; × (3) Adhesive strength Normal condition: Asphalt board (30cm x 30cm x 5
cm), each color paving material was applied twice with a metal trowel to a thickness of about 1 mm, and after being left to air dry at room temperature for 7 days, the tensile strength was measured using a Kenken type adhesion tester. Water resistance: Each color paving material was painted under the same conditions as the normal adhesive strength described above, left at room temperature for 7 days, air-dried, and then left in water at room temperature for 2 days, after which the tensile strength was measured using a Kenken type adhesion tester. (4) Abrasion resistance Normal state: Paint each color paving material to a thickness of about 1 mm using a metal trowel on a round slate plate with a diameter of about 10 cm, leave it at room temperature for 7 days, and after air drying, measure the taper index using a taper type abrasion tester. mg/100 revolutions was measured. (According to JIS K5665) Water resistance: Paint each color paving material under the same conditions as the normal abrasion resistance above, leave it at room temperature for 7 days, let it dry naturally, leave it in water at room temperature for 2 days, and then test it with a taper type abrasion tester. index
mg/100 revolutions was measured. (5) Weather resistance (according to JIS K5400) Each color paving material was applied to a slate board (10 cm x 5 cm x 0.5 cm) with a metal trowel to a thickness of approximately 1 mm, left at room temperature for 7 days, and after air drying, accelerated weather resistance test by WOM was performed. The colored pavement material was observed after 600 hours and judged based on the following criteria. Discoloration: △, no abnormality; 〇(6) Oil resistance Each color paving material was painted twice with a metal trowel on an asphalt board (30 cm x 30 cm x 5 cm), and the thickness was approx.
mm, left at room temperature for 7 days, air dried, then immersed in white kerosene for 24 hours, and visually observed their appearance to determine the presence or absence of abnormalities. That is, no abnormality; 〇, abnormality such as swelling or whitening; △ [Table]

Claims (1)

[Claims] 1 (1) Acrylic acid ester 44-96% by weight (2) Methacrylic acid ester and/or styrene
0 to 55% by weight (3) One or more selected from glycidyl methacrylate, N-methylol acrylamide, acrylamide, and glycidyl acrylate 0.1
~5% by weight (4) Unsaturated carboxylic acid 0.5~5% by weight Emulsion copolymer emulsion solid content containing the monomers (1) to (4) above as constituent units 100 parts by weight, film forming aid 1 ~20 parts by weight, 250-650 parts by weight of aggregate, 5 parts by weight of coloring pigment
Colored paving material consisting of ~30 parts by weight and 0.5 to 3 parts by weight of dispersant.