JPS6117869B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to road marking or floor coating compositions. Known resins used for coating road and floor surfaces such as concrete and asphalt include various solvent-based resins, unsaturated polyester resins, and epoxy resins, but these are difficult to apply thickly in one coat. Yes, but durability is low. In addition, products using hot-melt thermoplastic resins such as petroleum resins and rosin-based resins tend to crack from winter to early spring, causing small pieces to peel off from the cracks, and are extremely susceptible to chains. There is also the problem of poor safety because it is heated to 200 to 250°C during coating. On the other hand, conventional on-site polymerization type resins have the disadvantage that the curing time is long, which increases the time when roads are closed to traffic, which tends to cause traffic congestion, and if the curing time is forcibly shortened, they tend to become dirty after traffic resumes. The present inventors have studied to overcome these drawbacks and develop an in-situ polymerization type composition for road markings and floor coatings that can be applied thickly in one coat, has a short curing time, is resistant to staining, and has good durability. As a result of repeated efforts, we have arrived at the present invention. The present invention is a filler 1 whose main components are 100 parts by weight of a resin phase consisting of the following (A) to (D) and an aggregate with an average particle size of 10 μ or more and an oil absorption of 25 c.c. linseed oil/100 g or less. ~
1,900 parts by weight of a road marking or floor coating composition. (A) 40 to 95% by weight of at least one acrylic ester and/or methacrylic ester; (B) vinyl chloride-vinyl acetate copolymer and/or vinyl chloride-maleic ester copolymer 5
5-60% by weight of a polymer consisting of ~100% by weight and 95-0% by weight of a polymer or copolymer soluble in (A), (C) in a total of 100 parts by weight of (A) and (B). 0.1 to 10 parts by weight of a compound having at least two polymerizable double bonds in one molecule; and/or wax
0.1 to 5 parts by weight. In the present invention, part of the 5 to 60% by weight of component (B) can be replaced with a plasticizer soluble in (A) within a range of 30% by weight or less of (A) + (B). Examples of the acrylic ester of component (A) include methyl acrylate, ethyl acrylate, and butyl acrylate, and examples of the methacrylic ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, and methacrylate. Examples include 2-ethylhexyl acid, but especially those with a homopolymer glass transition temperature of 80
℃ or higher monomers such as methyl methacrylate and 0
C. or less with monomers such as 2-ethylhexyl methacrylate are advantageous. Among component (B), vinyl chloride-vinyl acetate copolymer and vinyl chloride-maleate ester copolymer are
It is necessary to be soluble in component (A), and among component (B), polymethyl methacrylate, methyl methacrylate, and (co)polymers that are soluble in (A) can be used as necessary. -2-ethylhexyl methacrylate copolymer and the like. These components (B) are added for the purpose of controlling the viscosity of the resin phase, shortening the polymerization time due to the presence of the polymer component, and increasing the notch strength. Examples of the plasticizer that can be substituted as part of the component (B) include chlorinated paraffin, polypropylene glycol, phthalate esters such as dibutyl phthalate and dioctyl phthalate, dioctyl adipate, dioctyl sebacade, and the like. These are added as necessary for the purpose of adjusting the viscosity of the resin phase or improving the conformability to road surfaces by plasticizing the cured product. (C) component is ethylene glycol di(meth)
acrylate, alkanediol di(meth)acrylates such as 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, Polyoxyalkylene glycol di(meth)acrylate such as propylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate ,
Examples include allyl (meth)acrylate and diallyl fumarate, which may be used alone or in combination of two or more. These (C) components are added for the purpose of crosslinking (A) and (B) and improving durability. Component (D) includes paraffin wax, polyethylene wax, and higher fatty acids such as stearic acid and 12-hydroxystearic acid, but two or more types having different melting points can also be used in combination. These components (D) are added for the purpose of blocking air during polymerization on the surface of the coating film, imparting gloss to the cured surface, and improving stain resistance. In the present invention, in order to improve the weather resistance of the composition, it is preferable to add an ultraviolet absorber in an amount of 0.005 to 5 parts by weight per 100 parts by weight of the total amount of (A) and (B). As ultraviolet absorbers, benzophenone derivatives such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-alkoxybenzophenone;
Examples include benzotrials such as (2'-hydroxy-5'-methylphenyl)benzotriazole. In addition, in the present invention, a silane cup is added in an amount of 10 parts by weight or less per 100 parts by weight of the total amount of (A) and (B) for the purpose of improving the adhesiveness to the road surface and the durability of the adhesive strength with the filler. It is preferred to add a ring agent. Typical silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyl. Examples include trimethoxysilane. The aggregate used in the present invention with an average particle size of 10 μ or more and an oil absorption of 25 c.c. Examples include powder and glass beads. When using aggregate with an average particle size of 10 microns or less or an oil absorption amount of more than 25 c.c. Hardening does not occur. This absorbs the surrounding soil, sand, and dust and becomes dirty, causing the white parts to quickly turn black and gray. This drastically reduces its practical value. In addition to the aggregate, the filler accounts for 1 to 50% of the total filler.
It is preferable to include a colored pigment or dye in a range of % by weight, and it is essential to add it especially when the purpose is to use for road marking. As such pigments and dyes, titanium oxide, barium sulfate, carbon black, chrome vermilion, Bengara, ultramarine, cobalt blue, phthalocyanine blue, phthalocyanine green, etc. are used. In the present invention, it is necessary to blend 100 parts by weight of the resin phase as described above and 1 to 1900 parts by weight of a filler. If the amount of filler is less than 1 part, not only will the strength decrease, but the degree of coloring will be too light, especially for road marking purposes, and if it is more than 1,900 parts, the surface will lose its luster and become easily stained. , resulting in disadvantages such as reduced strength. especially
A range of 100 to 500 parts by weight is preferred. The composition of the present invention can be cured within two hours using known redox catalysts at temperatures ranging from -30°C to 50°C. Although various types of redox catalysts can be used, it is advantageous to use a combination of a tertiary amine and an organic peroxide. The tertiary amine preferably has at least one aromatic residue bonded directly to the nitrogen atom. A small amount of a polymerization inhibitor such as hydroquinone can also be added to improve the storage stability of the resin phase. Furthermore, the composition of the present invention can also be used as a two-component type (base agent and curing agent) depending on the convenience of the coating method. In the following examples, parts represent parts by weight. Example 1 Methyl methacrylate 40 parts 2 Ethylhexyl acrylate 20〃 Chlorinated paraffin (Cl content 40%) 20〃 Tinuvin P (ultraviolet absorber, manufactured by Ciba Geigy) 0.25〃 Ethylene glycol dimethacrylate 2.0〃 n-paraffin (m After heating the mixture of 0.5〃 to 50℃ and stirring, 20 parts by weight of vinyl chloride/vinyl acetate (VC/VAC=75/25) copolymer was added little by little and dissolved. While cooling, 1.5 parts of N,N-dimethyl-P-toluidine was added. Next, add 40 parts of this resin phase to quartz sand (75~
After mixing 50 parts of titanium oxide (105 microns) and 10 parts of titanium oxide and stirring thoroughly, 0.8 parts of benzoyl peroxide was added and quickly applied to the concrete road surface to a thickness of about 3 mm. It cured in 15-20 minutes after addition. Approximately 30 minutes after construction, traffic resumed, and the construction surface was observed 6 months later, and found that there was almost no dirt and good whiteness was maintained, and there were no defects such as cracks or splits. Example 2 Methyl methacrylate 45 parts 2 Ethylhexyl acrylate 15〃 Chlorinated paraffin (C chlorine content 40%) 20〃 Tinuvin P (ultraviolet absorber, manufactured by Ciba Geigy) 0.25〃 Ethylene glycol dimethacrylate 2.0〃 n-paraffin ( 1) m.p58~60℃ 0.5〃 (2) m.p64~66℃ 0.5〃 Vinyl chloride/vinyl acetate copolymer (VC/VAC=75/25) 20〃 N,N-di( A resin phase solution was formed in the same manner as in Example 1 using 1.5〃 of 2-hydroxypropyl) -P-toluidine, and 40 parts of silica sand (0.5 mmφ) and calcium carbonate #SS30 (average particle size) were added to 40 parts of this solution. 13 micron oil absorption 21.4 cc linseed oil / 100 g, Nitto Funka Kogyo Co., Ltd.) 10 parts Titanium oxide (Ishihara Sangyo Co., Ltd.) After thorough stirring, 0.8 parts of benzoyl peroxide was added and the mixture was applied to the asphalt road surface to a thickness of approximately 2 mm. When applied to the desired temperature, it cured in 10 to 15 minutes at 35°C. Traffic resumed 25 minutes after construction, and the construction surface was observed 6 months later, and found to maintain good whiteness and no defects such as cracks, wrinkles, or splits. Comparative Example 1 Calcium carbonate, #SS30 was replaced with #NS200 (average particle size 23 microns, oil absorption 27c.c. linseed oil/100g), but the construction was carried out in the same manner as in Example 2. The construction was completed 6 months later. The surface was quite dirty and the whiteness had decreased considerably. Example 3 Methyl methacrylate 40 parts Lauryl methacrylate 15〃 Chlorinated paraffin 20〃 2-Hydroxy-4-octoxybenzophenone 0.25〃 Tetraethylene glycol dimethacrylate 2.0〃 N-paraffin (m.p 64-66℃) 0.5〃 Vinyl chloride/vinyl acetate copolymer (VC/VAC=75/25) 20〃 Polymethyl methacrylate (average degree of polymerization 650) 5〃 N,N-dimethyl-P-toluidine 0.5〃 γ-methacryloxypropyl tri A resin phase solution was formed using methoxysilane 1.0 in the same manner as in Example 1, and 30 parts of silica sand (0.5 mmφ), 10 parts of titanium oxide, and 25 parts of glass beads (0.4 mmφ) were added to 35 parts of this solution. After mixing and adding 0.35 parts of benzoyl peroxide and dissolving it uniformly, it was applied to a concrete road surface to a thickness of about 1.5 mm, and it hardened after about 15 minutes at 25 degrees Celsius, resulting in a well-whitened surface. was gotten. Traffic resumed 30 minutes after construction, and even after 6 months, it maintained good whiteness and no defects occurred. Comparative Example 2 Zinc white (particle size) was used instead of the silica sand used in Example 3.
When the construction was carried out in the same manner as in Example 3 except for using a coating material (0.5 micron), the construction surface became blackish gray after one month, and was still dirty even after one year. Example 4 Methyl methacrylate 45 parts Butyl acrylate 20〃 Polypropylene glycol (molecular weight 1000) 15〃 2,4-dihydroxybenzophenone 0.2〃 1,6-hexanediol diacrylate 3〃 Paraffin (1) m.p54-56℃ 0.5〃 (2)m.p68~70℃ 0.5〃 Vinyl chloride/vinyl acetate copolymer (VC/VAC=75/25) 20〃 N,N-di(2-hydroxypropyl) -P- A homogeneous resin phase solution was formed using toluidine 20〃 in the same manner as in Example 1, and 40 parts of this solution was mixed with quartz sand (average particle size 75
~105 micron) 40 parts, calcium carbonate #SS30
(Average particle size 13 microns, oil absorption 21.4cc linseed oil/
100g), 10 parts of titanium oxide and 0.4 part of benzoyl peroxide, and after uniformly dissolving,
When applied to an asphalt road surface to a thickness of approximately 2 mm, it cured in approximately 12 minutes at 20°C. 30 years after construction
Traffic was resumed within minutes, and the construction surface was observed 6 months later, and it maintained good whiteness and no defects occurred. Comparative Example 3 Talc (particle size approximately 3 microns) was used in place of the quartz sand and calcium carbonate #SS30 in Example 4, and the construction method was exactly the same as in Example 4. Two weeks later, the surface was stained black and gray. Ta. The same stain remained even after 6 months. Example 5 Methyl methacrylate 40 parts Stearyl methacrylate 20〃 Chlorinated paraffin 20〃 Vinyl chloride/vinyl acetate copolymer (VC/VAC=75/25) 20〃 1,6-hexanediol Dimethacrylate 4〃 Paraffin ( m.p54-56℃) 1.0〃 N,N-di(2-hydroxypropyl)-P-toluidine 3.0〃 Tridecyl phthalate 0.25〃 2-Hydroxy-4-octoxybenzophenone 0.2〃 Hydroquinone Performed using 20ppm A uniform resin phase solution was formed in the same manner as in Example 1, and 40 parts of this solution was mixed with quartz powder (average particle size 60
Micron), 10 parts of titanium oxide were added and mixed, 0.8 parts of benzoyl peroxide was added and dissolved uniformly, and the coating was applied to an asphalt road surface to a thickness of 2.0 mm at 22℃. It hardened in 10 minutes. Traffic resumed 20 minutes after construction, and even after 6 months, it maintained good whiteness and no defects occurred. Comparative Example 4 When alumina (average particle size 4.5 microns) was used instead of quartz powder (average particle size 60 microns) and the other conditions were the same as in Example 5, the whiteness of the applied surface decreased considerably after 6 months. It was black and gray and white. Example 6 Methyl methacrylate 45 parts Butyl acrylate 15〃 Chlorinated paraffin (Cl content 40%) 20〃 Tinuvin P 0.25〃 Tetraethylene glycol diacrylate 1.0〃 Divinylbenzene 1.0〃 n-paraffin (m.p54-56℃) 0.5〃 mixture was heated to 50℃, and while stirring, vinyl chloride/dimethyl maleate (VC/DMM=60/
40) After adding 20 parts of the copolymer little by little and making a solution, 1.5 parts of N,N-dimethyl-p-toluidine was added while cooling. Next, 40 parts of quartz sand (75 to 105 microns), 10 parts of calcium carbonate #SS30, and 10 parts of titanium oxide were thoroughly stirred into 40 parts of this resin phase.
Add 0.4 part of benzoyl peroxide and stir.
One month later, the concrete floor was applied to a thickness of approximately 2 mm, and the temperature was 30 to 45 at 30℃.
Hardened in minutes. I stepped on it with my shoes on 60 minutes after construction, and there was almost no dirt, it maintained its whiteness, and there were no defects such as cracks, wrinkles, or splits. Examples 7, 8, 9 Ethyl methacrylate 50 parts Methyl acrylate 10〃 Chlorinated paraffin (Cl content 40%) 20〃 Tinuvin P 0.25〃 n-paraffin (m.p54-56℃) 0.3〃 n-paraffin (m. Add component (C) in the proportions shown in Table 1 to the mixture of .p60~64℃) 0.2〃, mix, heat to 50℃, and add vinyl chloride/vinyl chloride/
After adding and dissolving 20 parts of dimethyl maleate (VC/DMM=60/40) copolymer in small portions, 1.5 parts of N,N-dimethyl-p-toluidine was added and dissolved while cooling. Next, 50 parts of quartz sand (75 to 105 microns), 5 parts of calcium carbonate #SS30, and 5 parts of titanium oxide were added to 40 parts of this resin phase, and after adding 0.4 parts of benzoyl peroxide and stirring, it was applied two weeks ago. When applied to a concrete floor surface to a thickness of approximately 2 mm, it hardened in 35 to 45 minutes at 30°C. I stepped on it with my bare feet 60 minutes after construction, and there was almost no dirt, it maintained its whiteness, and there were no defects such as cracks, wrinkles, or splits. 【table】

Claims (1)

[Scope of Claims] 1 100 parts by weight of a resin phase consisting of the following (A) to (D) and linseed oil with an average particle size of 10 μ or more and an oil absorption of 25 c.c.
Filler 1 to 1900 whose main component is aggregate less than 100g
A road marking or floor coating composition comprising parts by weight. (A) 40 to 95% by weight of at least one acrylic ester and/or methacrylic ester; (B) vinyl chloride-vinyl acetate copolymer and/or vinyl chloride-maleic ester copolymer 5
5-60% by weight of a polymer consisting of ~100% by weight and 95-0% by weight of a polymer or copolymer soluble in (A), (C) in a total of 100 parts by weight of (A) and (B). 0.1 to 10 parts by weight of a compound having at least two polymerizable double bonds in one molecule; (D) paraffin having a melting point of 50°C or higher relative to 100 parts by weight of the total amount of (A) and (B); /or wax
0.1-5 parts by weight