FI73454C - FOERFARANDE FOER FRAMSTAELLNING AV EN KOMPOSITION FOER VAEGMARKERING. - Google Patents

Description

1 73454

A method of making a road marking composition

The present invention relates to a process for preparing a polymer-based road marking composition.

The present invention can be advantageously used to denote traffic roads (such as center lines, guardrails, pedestrian columns, etc.) on asphalt roads, streets and squares that promote traffic safety.

Experience gained both at home and abroad 10 shows that high-quality road markings tend to reduce the incidence of road accidents: road markings by 17%; at intersections. 60%; and pedestrian deviation markings by 24%.

The most commonly used road sign-15 fillers in the world fall into three categories, namely: (1) thermoplastic marking compositions applied to the road surface in a molten state; (2) road marking paints in the form of dispersions, which are applied to the road surface by air spraying and which in turn can be subdivided as follows: (a) one-component thermoplastic systems; and (b) two-component thermoplastic systems; (3) thermoplastic strips used for road marking work by gluing them to the road surface with non-drying adhesives 25.

Thermoplastic coating compositions are the most widely used. The thermoplastic marking composition contains a polymeric, variable natural binder, pigments, fillers and special additives such as plasticizers, stabilizers and the like.

One known labeling composition is the substance of the trade name Chemie Ferdinand Heinrich Bituleit, "Bituleit", which contains a thermoplastic resin and glass fibers, the glass fiber content not exceeding 30% by weight (DE patent 2,302,065, 35 issued March 15, 1974).

2 73454 "Bituleit" marking composition gives coatings with good water resistance but low abrasion resistance and low coefficient of friction.

Another marking composition currently widely used is the trade name Nicolafrenz "Nilaplast", the binder of which comprises a mixture of polystyrene and styrene oligomeric homologues (DE patent 1,291,434, published September 8, 1974).

The molten "Nilaplast" needs as much as 80 10 minutes after application to reach a fully cured state, disrupting car traffic for the same amount of time.

Other previously known labeling compositions are the substance "Cleansol" under the trade name Svenska AB Cleansol. This includes cycloaliphatic and bisphenol-A-based epoxy resins as binders, as well as fillers and pigments (SE Patent 341,873, published January 17, 1972).

The main points of this material are low softening point (28-30 ° C), short lifespan (1-2 years), low adhesion to asphalt and low coefficient of friction. In order to increase the infection on the road surface, the road must be pretreated with a special compound.

A road marking composition is also known in which the binder is a mixture of a polyester resin with an acrylic, xylene, epoxy or vinyl chloride resin (JA patent 8,925, published June 5, 1974). The polyester resin used in this composition may be: (a) condensation products of polybasic acids such as terephthalic or isophthalic acids or their esters with lower alcohols and polyhydric alcohols; or (b) polyhydric alcohols (n ^ 3) and polybasic acid and aromatic monobasic acid.

The process for preparing the binder involves the synthesis of a polyester resin component, which involves a high energy consumption due to the fact that the temperature requirement is as high as 230-240 ° C. In addition, the polycondensation reaction takes place only in the presence of a catalyst, which li.

3 73454 is technologically a complicating factor. In the synthesis of the road marking composition, the binder uses raw materials intended for the production of high-strength fibers used in important industries. The low acid number of the polyester resin 5 (5.5 mg KOH / g) prevents a sufficiently good adhesion between the marking composition and the asphalt concrete surface of the road. Insufficient flexibility of a binder based on such a polyester resin prevents the desired strength and fracture resistance from being obtained in the coating, necessitating the use of expensive plasticizers which are included as additives in the labeling composition.

It was an object of the present invention to provide a process for preparing a road marking composition by selecting such process conditions in the binder preparation and mixing such a sequence with other components of the binder composition that it is possible to obtain a road marking composition characterized by good physical properties and good performance.

To achieve the above object, a method for preparing a road marking composition has been invented, which method comprises mixing the binder as a melt in at least one pigment and fillers.

The invention is characterized in that a saturated polyester resin having an acid number of 15 to 100 mg KOH / g and obtained from phthalic anhydride and at least one aliphatic glycol is used as a binder, and that the binder is first mixed with the pigment and then the fillers are added to the mixture thus formed.

When a polyester resin prepared by polycondensing the above-mentioned components is used as a binder, a labeling composition having high abrasion resistance, good adhesion and low water absorption results. The flexibility of the polyester resin chain allows the labeling composition to be prepared without the use of expensive plasticizers. The reactivities of the components selected for the synthesis of polyester-35 resins are such that the polycondensation reaction can be carried out at temperatures as low as 120-180 ° C. Reducing the acid number of the polyester resin below 15 mg KOH / g is not recommended as this would result in a label with increased brittleness, while increasing the acid number above 100 mg KOH / g would result in reduced water resistance.

To prepare the polyester resin, 1.2 moles of aliphatic glycols are taken per mole of phthalic anhydride from the group consisting of, for example, ethylene glycol, propylene glycol and butene glycol. The resulting polyester resin is amber in color and has an acid number of 15-50 mg KOH / g as a solid.

White pigments that can be used include lithopone, zinc oxide (ZnO), lead white titanium dioxide (TiO2) of the rutile or anatase type. Cadmium pigments (golden yellow, dark yellow and lemon yellow), lead chromate, zinc chromate and strontium chromate as well as other pigments added to red, green, blue and black to obtain 20 can be used as color pigments.

Rutile-type titanium dioxide is the most important of the white pigments because it has good coverage.

Lithopone is a mixture of ZnS (30%) and BaSO 4 (70%) with a lower coverage than titanium dioxide.

Zinc oxide is a bright white pigment with high coverage, but like lead white, it has limited use due to its interaction with the functional groups in the polyester resin, resulting in a controlled melt viscosity of the labeling composition li-30.

Insoluble dry inorganic materials are useful as fillers, for example, white quartz sand (SiO 2) with a particle diameter of 0.1 to 0.5 mm, marble powder (CaCO 2) with a particle diameter of 0.1 to 35 mm, glass beads, dolomite (CaCO 2 .MgCO 2), chalk (CaCO 2), kaolin (ΑΙ- ^ Ο ^. 2SiO 2 .2H 2 O), talc (4SiO 2 -H 2 O), or barite (BaSO 4).

5 73454

The mixing of the components can be performed in a reactor or a horizontal type mixer as well as in the boiler of the road marking machine immediately before the application of the marking composition.

5 The quality of a road marking composition based on polyester resin depends to a large extent on the order in which the components are charged.

The first step in the process of the invention is to mix the polyester resin and the pigment by chemically reacting the pigment with the carboxyl groups of the polyester resin to form surfactants with good wetting properties. This is followed by the successive or alternating addition of marble powder and sand.

15 Changing the mixing order of the components results in poor mixing of the resin and additives and insufficient homogeneity of the mixture.

The mixing of the components is best carried out at a temperature of 100-200 ° C. Mixing temperatures below 100 ° C affect homogenization due to the high viscosity of the melt, while temperatures above 200 ° C can cause deterioration of the binder and consequently deterioration in the physical properties of the road marking agent and deterioration of the color of the substance.

25 Table 1 below shows the different proposed road marking compositions.

The present invention is practiced as follows.

The saturated polyester resin 30 used as a binder is synthesized in advance.

The synthesis of the binder is carried out in a reactor equipped with a stirrer and a heating mantle. The polycondensation reaction is carried out in an inert gas stream in order to prevent the oxidation of the starting components and the oligomers formed in them at the beginning of the synthesis.

The temperature range of the synthesis is 120-180 ° C. When charged with phthalic anhydride and an aliphatic glycol or a mixture of glycols, the reactor temperature is raised to 120 ° C for two hours to effect precondensation. The reaction temperature is then raised to 160-180 ° C and the polycondensation is carried out until the desired acid number is reached. The process is controlled by taking resin samples to determine the acid number.

The next step is to prepare the road marking composition by mixing the pigments and fillers in the polyester.

The polyester resin, preheated to 120 ° C, is fed through a heated conduit to a weighing charge device for measurement in a mixer surrounded by a heating mantle and equipped with a stirrer. The pigment is then added to the polyester resin melt at 120 ° C in a mixer and the mixture is stirred for one hour.

This is followed by raising the temperature of the reaction mass to 200 ° C and adding the marble powder and sand sequentially while the mixer is running. After the components have been charged, the mass is stirred at 200 ° C for a further 30-40 minutes. At the end of the mixing process, the final label-20 composition is cooled to 130-140 ° C and poured into molds pretreated with a release agent. After the marking composition has completely cooled in air, it is placed in storage or used for road marking.

The quality control of the final product examines the wear resistance of 25 products, determined as the weight loss that occurs in the sample after 5,000 revolutions of the abrasive disc; in addition, the diffuse reflection coefficient of the labeling composition and the water absorption are determined.

The process according to the present invention for the preparation of road marking compositions makes it possible to obtain a wear-resistant marking material which has good adhesion to asphalt concrete or concrete and low water absorption. The technology used is remarkably simple.

The use of reactive starting materials for the synthesis of polyester-35 resins makes it possible to carry out the polycondensation reaction at a relatively low temperature and without the use of catalysts.

73454

When the polycondensation is carried out at a temperature of 120 to 180 ° C, the polyester resin obtained is light in color and thus allows reduced pigment concentrations.

Example 1 5,100 parts by weight of a polyester resin having an acid number of 33 mg KOH / g were charged to a mixer and the heating was switched on. When the temperature of the resin had reached 100-120 ° C, 91 parts by weight of lithopone was added to the resin. After stirring for 30 minutes, the temperature of the pulp was raised to 150-160 ° C and 172.5 and 91 parts by weight of marble powder (particle diameter 0.1-1.6 mm) and quartz sand were added. Stirring of the components was then continued at 160-165 ° C for two hours.

The marking composition had the following component ratios by weight: polyester resin 22.0 lithopone 20.0 marble powder 38.0 quartz sand 20.0 The above road marking composition was tested to give the following results: diffusion reflectance 75%; consumption 0.007 to 0.01% and water resistance 0.5%.

Example 2 The manufacturing process and consumption rates of the components of this labeling composition were essentially the same as in Example 1.

The polyester resin used had an acid number of 40 mg KOH / g. The diffusion reflection coefficient was 75%, consumption 0.1% 30 and water absorption 0.7%.

Example 3 The consumption rates of the components of this road marking composition manufacturing process were substantially the same as in Example 1.

The acid number of the polyester resin used was 27 mg KOH / g.

The diffusion reflection coefficient was 65%, consumption 0.01% and water absorption 0.4%.

8 73454

Example 4 The manufacturing process and consumption rates of the components of this road marking composition were essentially the same as in Example 1.

The road marking composition contained a polyester with an acid number of 15 mg KOH / g.

The coefficient of diffusion reflection was 60%, water absorption 0.2%. Consumption was not prescribed, the composition was too brittle.

Example 5 The manufacturing process of this road marking composition and the consumption rates of the components were essentially the same as. in Example 1.

The road marking composition contained a polyester with an hap-15 pathway of 100 mg KOH / g.

The diffusion reflection coefficient was 75% and the water absorption was more than 5%. Consumption was not determined because the coating surface was sticky.

Example 6 20,100 parts by weight of a polyester resin having an acid number of 32 mg KOH / g was charged to a mixer. 22.7 parts by weight of titanium dioxide were added at 100 ° C. After stirring for 0.5 hours, 240 parts by weight of marble powder and 91 parts by weight of white quartz sand were added and stirring was continued at 100 ° C for one hour.

The road marking composition had the following component ratios in weight percent: polyester resin 22 titanium dioxide 5 30 marble powder 53 quartz sand 20

The diffusion reflection coefficient was 70%, consumption 2% and water absorption 2.5%.

li 9 73454

Table 1 SI. Components, 1 234567 8

No. Mass part 5 1. Dust ester resin 100 100 100 100 100 100 100 100 2. Lithopone 91 91 91 91 91 - 91 3. Titanium dioxide - - - - - 22.7 - 22.7 4. Marble powder 172.5 172.5 172 .5 172.5 172.5 172.5 172.5 240 5. Quartz sand 91 91 91 91 91 91 91 91 10 6. Color pigments - - 9 10 11 12 13 14 15 16 17 18 19 20 100 200 100 100 100 100 100 100 100 100 100 100 15 100 100 91 91 91 91 136.3 100 - 91 ------- 45.5 - - 38.6 - 200 100 131.8 - 263.6 68.1 130 218 66 , 6 84 172 172.5 100 100 131.8 263.6 - 195.4 91 91 66.6 91 91 91 --------- 6.8 6.8 - 20

Example 7 The manufacturing process and consumption rates of the components of this road marking composition were essentially the same as in Example 1.

The stirring temperature was 200 ° C. Partial deterioration of the substance was observed at this temperature.

The diffusion reflection coefficient was 50%, consumption 0.01% and water absorption 0.8%.

Example 8 The manufacturing process of this road marking composition was essentially the same as in Example 1, the composition containing the components in the same proportions as in Example 6. The consumption rates of the components in weight percent were 100, 22.7, 240 and 91%.

35 The diffusion reflection coefficient was 75%, consumption 0.007 to 0.01% and water absorption 0.1%.

_ - T; ___ 10 73454

Example 9

A polyester resin having an acid number of 32 mg KOH / g was mixed with the other components following the process of Example 1.

5 The road marking composition had the following component ratios in weight percent: polyester resin 20 lithopone 20 marble powder 40 10 quartz sand 20

The consumption amounts of the components in parts by weight were 100, 100, 200 and 100, respectively.

The diffusion reflection coefficient was 75%, consumption 0.005% and water absorption 0.3%.

15 Decreased fluidity was observed when the composition was placed on the road surface.

Example 10 The manufacturing process of this road marking composition was essentially the same as in Example 1.

20 The road marking composition contained the proportions of the components by weight: polyester resin 40 lithopones 20 marble powder 20 25 quartz sand 20

The consumption amounts of the components by weight were 200, 100, 100 and 100, respectively.

The diffusion reflection coefficient was 60%, consumption 0.1% and water absorption 1.2%.

30 Example 11

The manufacturing process of the road marking composition was essentially the same as in Example 1.

In the road marking composition, the components had the following weight ratios in weight percent: 73454 polyester resin 22 lithopones 20 marble powders 29 quartz sand 29 5 The consumption amounts of the components were 100, 91, 131.8 and 131.8 by weight, respectively.

The diffusion reflection coefficient was 75%, consumption 0.01% and water absorption 0.7%.

Example December 10 Tiemerkintäkoostumuksen completion of the process was substantially the same as in Example 1.

In the road marking composition, the components had the following ratios in weight percent polyester resin 22 15 lithopones 20 quartz sand 58

The consumption amounts of the components by weight were 100, 91 and 263.6, respectively.

The diffusion reflection coefficient was 75%, consumption 1.1% 20 and water absorption 1.5%.

Example 13

The manufacturing process of the road marking composition was essentially the same as in Example 1.

In the road marking compositions, the components had the following ratios in weight percent: polyester resin 22 lithopones 20 marble powders 58

The consumption amounts of the components by weight were 100, 91 and 263.6, respectively.

The diffusion reflection coefficient was 75%, consumption 0.01% and water absorption 0.5%.

Example 14

The process for preparing the road marking composition was essentially the same as in Example 1.

12 73454

In the road marking composition, the components had the following proportions by weight: polyester resin 22 lithopones 20 5 marble powder 15 quartz sand 43

The consumption amounts of the components by weight were 100, 91, 68.1 and 195.4, respectively.

The diffusion reflection coefficient was 75%, consumption 0.01 10% and water absorption 1.2%.

Example 15

The manufacturing process of the road marking composition was essentially the same as in Example 1.

In the road marking composition, the components had the following ratios in weight percent: polyester resin 22 lithopone 30 marble powder 28 quartz sand 20 20 The consumption amounts of the components in parts by weight were 100, 136.3, 130 and 91, respectively.

The diffusion reflection coefficient was 80%, consumption 0.01% and water absorption 0.5%.

Example 16 25 Tiemerkintäkoostumuksen the manufacturing process was substantially the same as in Example 1.

In the road marking composition, the components had the following ratios in weight percent: polyester resin 22 30 titanium dioxide 10 marble powder 48 quartz sand 20

The consumption amounts of the components by weight were 100, 45.5, 218.1 and 91, respectively.

35 The diffusion reflection coefficient was 80%, consumption 0.01% and water absorption 0.1%.

13 73454

Example 17

The process for preparing the road marking composition was essentially the same as in Example 1.

In the road marking composition, the components had the following ratios of 5% by weight: polyester resin 30 lithopones 30 marble powder 20 quartz sand 20 10 The consumption amounts of the components in parts by weight were 100, 100, 66.6 and 66.6, respectively.

The diffusion reflection coefficient was 80%, consumption 0.01% and water absorption 1%.

Example 18 15 Tiemerkintäkoostumuksen the manufacturing process was substantially the same as in Example 1.

In the road marking composition, the components had the following ratios in weight percent: polyester resin 22 20 yellow pigment (CdS) 1.5 lithopone 18.5 marble powder 38 quartz sand 20

The consumption amounts of the components in parts by weight were 100, 6.8, 84, 172 and 91, respectively.

The composition was yellow in color and had a consumption of 0.01% and a water absorption of 0.5%.

Example 19

The process for preparing the road marking composition was essentially the same as in Example 1.

In the road marking composition, the components had the following ratios in weight percent: polyester resin 22 yellow pigment (CdS) 1.5 35 titanium dioxide 8.5 marble powder 38 quartz sand 20 14 73454

The consumption amounts of the components in parts by weight were 100, 6.8, 38.6, 172 and 91, respectively.

The diffusion reflection coefficient was 75%, consumption 0.01% and water absorption 0.2%.

Example 20 100 parts by weight of polyester resin (acid number 32 mg KOH / g) were charged to a mixer and heating was switched on. When the temperature of the resin melt reached 120 ° C, 172.5 parts by weight of marble powder was added, and when the temperature of the mass was further raised to 165 ° C, quartz sand and lithopone were added in each of 91 parts by weight. Stirring was continued at 165 ° C for two hours.

“The resulting blend composition was inhomogeneous and loose.

15 In the road marking composition, the components had the following proportions by weight: polyester resin 22 lithopone 20 marble powder 38 20 quartz sand 20

The diffusion reflection coefficient was 55%, consumption 0.5% and water absorption 1.2%.

The properties of the road marking compositions obtained in Examples 1-20 are summarized in Table 2.

25 Table 2

Features Examples 1 2 3 4 5 6 7 8

Diffuse reflection coefficient 30,% 75 75 65 60 75 70 50 75

Wear,% 0.007 0.007 (after 5,000 revolutions) 0.01 0.01 0.001 - -2 0.01 0.01

Water absorption,% 0,5 0,7 0,4 0,2 5 2,5 0,8 0,1 35 9 10 11 12 13 14 15 16 17 18 19 20 75 60 75 75 75 75 80 86 80 - 75 55 0.005 0.1 0.001 1.1 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.5 0.3 1.2 0.7 1.5 0.5 1 2 0.5 0.1 1 0.5 0.2 1.2

Claims (2)

73454 A process for preparing a road marking composition, which process comprises mixing the binder as a melt in at least one pigment and fillers, characterized in that a saturated polyester resin having an acid number of 15 to 100 mg KOH / g and obtained from phthalic anhydride and at least one aliphatic glycol, and that the binder is first mixed with the pigment, after which fillers are added to the mixture thus formed. Process according to Claim 1, characterized in that the components are mixed together at a temperature of 100 to 200 ° C.