JPS6152186B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of making hot melt traffic paint formulations. Commonly used formulations for hot-melt traffic paints are paints that are solid at room temperature and consist of tackifying resins, plasticizers, pigments, fillers, and the like. The properties required for heat-melting traffic paint include short plasticization time, excellent melt fluidity, aggregate settling properties, and heat resistance stability during application, as well as heat resistance and stain resistance of the paint film after application. , excellent hair crack resistance, compressive strength, and yellowness. In recent years, hydrocarbon resins have been used as tackifying resins, but hydrocarbon resins alone are insufficient in both workability during construction and properties of the coating film after construction. The present invention relates to an improvement thereof, in which a composition consisting of a hydrocarbon resin, a specific olefin resin, a polyethylene wax, and a plasticizer is prepared in advance, and then mixed with other components to prevent melting during construction. This is based on the fact that a formulation for hot-melt traffic paint can be obtained in a short amount of time, and the paint film after application has excellent heat resistance and stain resistance. That is, the present invention provides an aliphatic hydrocarbon resin 100
0.5 to 10 parts by weight of a polyolefin resin having a melt index selected from the group of polyethylene, polypropylene, ethylene-propylene copolymer and ethylene-butene copolymer in the range of 4 to 100 g/10 minutes, molecular weight 1500 No
0.5 to 15 parts by weight of polyethylene wax 4000 and a plasticizer are melt-mixed to produce a granular, flaky or lump composition, and the composition is mixed with pigments, fillers, etc. at a temperature below the softening point of the composition. The present invention relates to a method for producing a formulation for hot melt traffic paint, characterized in that it is mixed at a temperature. The hydrocarbon resin used in the present invention is obtained by polymerizing a fraction containing aliphatic unsaturated hydrocarbons with a boiling point range of -20°C to +100°C obtained during thermal decomposition of petroleum products according to a conventional method. It is an aliphatic hydrocarbon resin obtained by The boiling point range is -
The aliphatic unsaturated hydrocarbon-containing fraction at 20°C to +100°C mainly contains C ₄ to C ₆ aliphatic unsaturated hydrocarbon components, such as C ₄ C ₅ fraction, C ₅ fraction,
There are _C5 fractions from which cyclopentadiene has been removed and _C5 fractions from which isoprene has been removed.
Preference is given to using aliphatic hydrocarbon resins produced by polymerizing C ₄ and C ₅ fractions. Furthermore, the aliphatic hydrocarbon resin used in the present invention is composed of the above-mentioned fraction and pure monomers capable of cationic polymerization, such as unsaturated fatty acids such as butene-1, isobutene, butadiene, diisobutylene, piperylene, dicyclopentadiene, etc. or alicyclic compounds, or styrene, vinyltoluene, α-
It may also be a resin obtained by copolymerizing an unsaturated aromatic compound such as methylstyrene or indene in a similar manner. The content of these copolymer components is preferably 50% by weight or less of the total weight, and the aromatic monomer component is particularly preferably in a small amount from the viewpoint of melt fluidity and weather resistance. Among these aliphatic hydrocarbon resins, those having a softening point (ring and ball method) of 80 to 120°C, a hue (Gardner) of 12 or less, an acid value of 0.2 to 50, and an iodine value (Wiss method) of 200 or less are preferable. , these may be modified with carboxylic acid, ester or polyhydric alcohol. The polyolefin resin used in the present invention is
Polyethylene, such as medium-low pressure polyethylene, high pressure polyethylene, etc., is selected from the group of polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, and the polyolefin resin is further added with acrylic acid, methacrylic acid, maleic acid, etc. It may be a graft copolymer of unsaturated carboxylic acids or derivatives thereof, such as acid anhydrides, esters, amides, imides, etc. These are polymers with an intrinsic viscosity ([η] 135°C, decalin solution) of 0.8 or more, preferably 1.0 to 2.5, and a melt index (190°C) of 4
to 100g/10 minutes. The polyethylene wax used in the present invention is
It is a wax-like substance that is solid at room temperature and has a molecular weight of 1,500 to 4,000. It is also possible to use modified waxes in which these waxes are further oxidized, chlorinated, sulfonated or grafted with unsaturated compounds, especially unsaturated carboxylic acids or derivatives thereof. Among these polyethylene waxes, polyethylene wax obtained by polymerization with a Ziegler type catalyst is particularly preferred, and has a carbon number of 1000.
A wax-like material with double bonds of 0.7 or less, preferably 0.5 or less per individual is suitable. The composition for hot-melt traffic paint of the present invention comprises 0.5 to 10 parts by weight of the polyolefin resin, 0.5 to 15 parts by weight of polyethylene wax, a plasticizer, and a pigment based on 100 parts by weight of the aliphatic hydrocarbon resin. and a filler are added. The plasticizer to be blended has a pour point of -5°C or lower, and includes mineral oil-based softeners, phthalic acid derivatives such as dibutyl phthalate, liquid paraffin, etc. The blending amount is 100% of the aliphatic hydrocarbon resin. It is preferably 2 to 10 parts by weight, particularly 20 to 100 parts by weight per 100 parts by weight of polyethylene wax.
It is preferable to mix parts by weight. Pigments usually include titanium white, zinc white, yellow lead, red iron oxide, phthalocyanine blue, etc. When titanium white is used, it has a synergistic effect of improving fluidity.
The amount of pigment blended is usually 2 to 200 parts by weight. Calcium carbonate, silica sand, cold water sand, talc, calcium sulfate, etc. are used as fillers, and the amount is usually 50 to 1000 parts by weight. In addition, a light-reflecting substance such as glass beads or cut glass or an anti-slip substance may be added as a filler, and the amount is usually 50 to 200 parts by weight. The amounts are based on 100 parts by weight of the aliphatic hydrocarbon resin. The traffic paint formulation of the invention includes:
If necessary, various stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, etc. can be added. Examples of these include 2,6-di-tert-butyl-p-cresol, tetrakis[methylene-
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4'-
Butylidene bis-(6-tert-butyl-m-cresol), ascorbic acid, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N・N-(bis-2-hydroxyethyl)alkylamine, 2- (2′-hydroxy-
Examples include 3',5'-tert-butylphenyl)-5-chlorobenzotriazole. These stabilizers and the like may be added to each component in advance, or may be added at the time of mixing. The aliphatic hydrocarbon resin, the polyolefin resin, the polyethylene wax, and the plasticizer are melt-mixed in advance to produce a composition in the form of granules, flakes, or blocks. It is preferable to prepare the composition so that the melt viscosity (at 200° C.) is 80 to 300 cp. The composition in the form of granules, flakes or blocks is mixed with a pigment, a filler and, if necessary, a plasticizer at a temperature below the softening point of the composition, preferably at room temperature, to form a formulation for hot melt type traffic paint of the present invention. Things are manufactured. The working viscosity (200° C.) of the hot melt traffic paint formulation provided by the present invention is from 2000 to 8000 cp, preferably from 3000 to 6000 cp. According to the method of the present invention, compared to the case where the entire amount of the traffic paint formulation is heated and melted and mixed,
Traffic paint formulations can be produced using less heat. In addition, compared to using a traffic paint composition obtained by mixing the entire amount at room temperature, not only is the time required for melting reduced, but the traffic paint composition has good thermal stability and prevents blocking due to surface welding. It can also suppress air oxidation of the plasticizer and can be effectively stored for a long period of time. The traffic paint formulation provided by the method of the present invention also improves the heat resistance of the paint film after application.
Shows excellent properties such as compressive strength and hair crack resistance. Examples are shown below. However, measurements and evaluations were conducted using the following methods. (i) Basic physical properties Softening point JISK2531 Acid value JISK5902 Pour point JISK2269 Melt index (MI) ASTMD1238 (190
℃) Molecular Weight The viscosity average molecular weight (Mv, unit: 10,000) was calculated from the intrinsic viscosity [η] 4 dl/g) measured in a decalin solution at 135°C using the following formula. [η]
=2.74×10 ^-4 Mv ^0.81 (ii) Physical properties of a composition consisting of a hydrocarbon resin, a polyolefin resin, a polyethylene wax, and a plasticizer Melt viscosity Measured at a temperature ^of 200 m by an EMILA rotational viscometer
Measured at a shear rate of 176 sec ^-1 . (iii) Physical properties of mixtures for hot-melt traffic paints (a) Working viscosity After the mixture for hot-melt traffic paints was heated to 200°C, it was measured using an EMILA rotational viscometer (manufactured by EMILA, Denmark). shear rate
Measured at 176sec ^-1 . (b) Melting time Hot-melt traffic paint formulations
600g in a stainless steel beaker (80mmφ×127
mm) and set it in a constant temperature oil bath at 190℃. Next, quickly stir the stirring rod (2 blades, width 12
mm, length 40 mm) and start stirring under a constant voltage (50 V) using a Heidon screw motor (model 1200RT/600RT). Paying attention to the current value, the melting time (min) was defined as the time from when the beaker containing the sample was placed in the thermostat until the current value stabilized. (c) Aggregate settling properties
The mixture was filled into a 50 ml beaker, left to stand at 240°C for 2 hours, cooled and hardened, cut vertically, and expressed as the sedimentation rate (%) of the filler on the cut surface. (d) Compressive strength of coating film Measured according to JISK5665. However, the compression speed was 50 mm per minute. (e) Hair cracks in paint film A test piece coated to a thickness of 1.5 mm on a tin panel (70 x 150 mm) was measured using a Sunshine Weatherometer (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63 ± 3°C. Spray 9min/hr,
An accelerated deterioration test was conducted under conditions of relative humidity of approximately 50% and irradiation time of 120 hours. As a result, changes in appearance were evaluated on the following four levels. A: No change B: Thin hair cracks appear. C: Thick hair cracks appear. D: Many thick hair cracks appear. A test piece was prepared according to the method described above, and the L, a, and b values were measured in a color studio. From these values, the whiteness W (%) = 100 - {(100 - L) ² + a ² + b ² } ^1
/2 was calculated. (g) Yellowness of paint film A white paint test piece was prepared from a hot-melt traffic paint formulation according to the method described in JIS K5665 5 and 6. After accelerated deterioration of this test piece using the method shown in (e),
The b value was measured in a color studio using the method shown in (f), and the degree of yellowness was expressed by this b value. (h) Stain resistance of paint film Test pieces were prepared from the hot-melt traffic paint formulation according to the method described in JIS K5665, 5 and 6. After 24 hours, a powder consisting of 95 parts by weight of red clay and 5 parts by weight of carbon black was sprinkled on the paint film, the powder was removed with a brush, and the whiteness of the paint film was measured according to (f). It is expressed as the retention rate (%) of whiteness after contamination. (g) Compression creep rate of paint film After melting the hot-melt traffic paint formulation, a test piece with a cross-sectional area of 4 cm ² and a height of 20 mm was prepared, and a compression creep test was conducted at a pressure of 230 g/cm ² and a temperature of 50°C. was carried out and expressed as the creep rate (% hr ^-1 ) at a deformation rate of 15%. Reference Examples 1 to 6 The composition ratios of aliphatic hydrocarbon resin, polyethylene wax, mineral oil, and polyolefin resin shown in Table 1 were melted and mixed at 190°C for 2 hours, and a thickness of 2.
A homogeneous composition in the form of flakes of mm was obtained.

【table】

[Table] Examples 1 to 5, Comparative Examples 1 to 5 Using the compositions prepared in Reference Examples 1 to 5, the compositions shown in Table 2 were mixed at room temperature to form ordinary welding type traffic paints. Melt this at 190℃,
The paint performance was evaluated after stirring and mixing for 30 minutes. The results are shown in Table 2 along with commercially available paints.

【table】

Claims (1)

[Scope of Claims] 1 100 parts by weight of aliphatic hydrocarbon resin, melt index selected from the group of polyethylene, polypropylene, ethylene-propylene copolymer and ethylene-butene copolymer from 4 to 100 g/
Melting and mixing 0.5 to 10 parts by weight of a polyolefin resin, 0.5 to 15 parts by weight of a polyethylene wax having a molecular weight of 1,500 to 4,000, and a plasticizer for 10 minutes to produce a granular, flaky or lump composition; 1. A method for producing a composition for hot-melt traffic paint, which comprises mixing the composition with pigments, fillers, etc. at a temperature below the softening point of the composition. 2. The manufacturing method according to claim 1, characterized in that the composition is mixed with pigments, fillers, etc. at room temperature.