KR20210018890A - Hot melt traffic lane tape - Google Patents

Abstract

The present invention relates to a hot-melt traffic lane tape for marking lanes, which uses a specific metal oxide to significantly increase the elongation property of paint, increases abrasion resistance, weather resistance, and retro-reflectivity required in the paint, increases a peeling strength through an increase of adhesive strength, and reduces curing time, thereby reducing a construction period and increasing workability. According to the present invention, the hot-melt traffic lane comprises: a paint layer containing a colorant and a curing agent for color expression in accordance with the purposes of the lanes; and an adhesive layer for adhering the paint layer in a coated and cured state to a surface of a road. The paint layer is manufactured by manufacturing polyamide resin, which is manufactured by condensing and polymerizing ethylenediamine with dimer acid prepared from at least one fatty acid selected from a group consisting of palm oil, tung oil, soybean oil, and castor oil to manufacture polyamide, graft-polymerizing 3 to 10 parts by weight of maleic anhydride to 100 parts by weight of the polyamide, and adding and mixing 1 to 2 parts by weight of a group 4 element-based complex compound to the graft-polymerized polyamide, and uniformly mixing: 15 to 30 parts by weight of the polyamide resin; 30 to 40 parts by weight of an extender; 2 to 15 parts by weight of a colorant; 1 to 2 parts by weight of wax; and 0.5 to 1.5 parts by weight of a heat stabilizer.

Description

Fused lane tape for road marking {HOT MELT TRAFFIC LANE TAPE}

The present invention relates to a lane tape that is fused to the road surface of a road, and more particularly, by using a specific metal oxide, the elongation characteristics of a paint are remarkably improved, and the peel strength by improving the wear resistance, weather resistance, and adhesive strength required for the paint. The present invention relates to a fusion-type lane tape for road markings that can increase construction time and improve workability by shortening the curing time as well as improving the increase and retroreflectivity.

On paved road surfaces such as general automobile roads or bicycle roads, information such as guidance of the direction of travel and speed limit or destination for drivers or pedestrians is displayed in various ways.

Typical road marking lines are defined as road marking paints (KS M 6018:2014), and can be classified into oil-based and water-based road sign paints, plastic paints for room temperature curing, and fusion-type road sign paints.

These road sign paints cannot close the construction site for a long time due to their characteristics, and the formed film is not only exposed to the external environment as it is, but also receives continuous mechanical force and friction. Therefore, various road sign paints are applied to the external environment with quick workability. Weatherability that can withstand is required as a basic requirement.

Oil-based paints are manufactured in liquid form after appropriately mixing acrylic or alkyd resin with organic solvents and pigments, and their use is restricted due to problems that cause air pollution, including volatile organic compounds (VOC). Since water-based paints are manufactured in a liquid form by mixing an emulsion resin with a pigment, etc., construction is limited and drying is slow.

In addition, oil-based paints and water-based paints are not preferable as paints for various road markings because the thickness of the paint becomes thinner after drying of the solvent and water, resulting in less wear layer.

On the other hand, fusion-type paints are manufactured in powder form by mixing a thermoplastic resin with a pigment, a filler, and a glass bead, and can be applied by heating and melting at the road site. Since it has this possible advantage, it is used as a paint for various road signs.

On the other hand, a lot of lane tapes have been developed that can complete the construction within a short time, have excellent adhesion to the road surface, and have excellent contamination resistance, and enable a driving driver to easily identify the alignment of the road even at night or in rainy weather.

In this regard, for example, in Korean Unexamined Patent Publication No. 1993-0021888, a non-woven fabric is adhered to the upper surface of a tape body composed of an aluminum thin plate, and a fluorescent display unit mixed with epoxy resin and glass powder is laminated thereon. A "road marking tape" is disclosed in which an adhesive layer is formed by applying an adhesive to the bottom surface of the tape body after heat-curing at a temperature and covering the adhesive surface with transfer paper.

However, since the tape uses a non-spherical (random type) glass powder as it is mixed with paint or resin, the retroreflective luminance rate is very low, and there is a problem in that the visibility of lanes at day and night is insufficient.

In addition, Patent No. 1163685 discloses that 3 to 5 parts by weight of an antifouling agent, 6 to 10 parts by weight of an elastic imparting agent, 25 to 40 parts by weight of a filler, 20 to 30 parts by weight of glass beads, and 3 parts by weight of an inorganic pigment in 6 parts by weight of the base resin. To 7 parts by weight, 05 to 1 parts by weight of an anti-settling agent, and 1 to 2 parts by weight of a viscosity modifier, the contamination inhibitor is a styrene acrylonitrile copolymer, and the elasticity imparting agent is 3 to 5 parts by weight of ethylene vinyl acetate and styrene butadiene. Consisting of 3 to 5 parts by weight of a styrene copolymer, the viscosity modifier is disclosed for a "fusion adhesive tape composition for road marking" comprising linseed oil or soybean oil.

In these existing tape compositions, there is a need to improve the adhesion between the binder and the glass beads and the wear resistance, and the adhesion is excellent not only to asphalt concrete (so-called ascon) but also to cement concrete, and the difference in thermal expansion coefficient according to temperature In order to prevent cracks in the coating film, products with excellent tensile strength and elongation at break are required.

Unexamined Patent Publication No. 1993-0021888 (published on November 23, 1993)-Road marking tape. Patent Publication No. 2019-0002015 (published on January 8, 2019)-Road lane marking tape and lane marking method using the same. Registered Patent No. 0740296 (registered on July 10, 2007)-Thermoplastic hot melt tape for road marking and construction method using the same. Registered Patent No. 1163685 (registered on July 2, 2012)-A fusion adhesive tape composition for road marking and its construction method.

The present invention has been made in view of the technical problems in the prior art, and the main object of the present invention is to improve the elongation characteristics of a paint by using a specific metal oxide, and abrasion resistance and weather resistance, which are general characteristics required for paints. , To provide a fusion-bonded lane tape for road markings that can improve peel strength and retroreflectivity by improving adhesive strength, and shorten the curing time to greatly improve construction and construction time.

The present invention for achieving the above object is to prepare a polyamide by condensation polymerization of ethylenediamine in a dimer acid prepared from one or more fatty acids selected from the group consisting of palm oil, tung oil, soybean oil and perm oil, and the polyamide 100 weight After graft copolymerization of 3 to 10 parts by weight of maleic anhydride to the part, 1 to 2 parts by weight of a Group 4 element-based complex compound is added and mixed to prepare a polyamide resin, and 15 to 30 parts by weight of this polyamide resin, 30 to 40 extender pigments Part by weight, 2 to 15 parts by weight of colorant, 1 to 2 parts by weight of wax, 0.5 to 1.5 parts by weight of heat stabilizer are homogeneously mixed to prepare a paint, and the paint is supplied to the surface of the drum and cooled to maintain a certain thickness. At the same time, it is manufactured by spraying glass beads evenly on the surface, pressing in, and curing.

In addition, the Group 4 element-based complex is reacted with a titanium ion source, a zirconium ion source, a hafnium ion source, a rudphonium ion source, or a combination thereof with a first chelating compound in a first reaction, and in a subsequent second reaction It may be a titanium, zirconia, hafnia, or rudphonium-based complex obtained by reacting with a secondary chelating compound.

In addition, the chelating compound is ethylenediaminetetraacetic acid, glycinate, ethylene diamine, aspartic acid, amino acid glycine, aminopolycarboxylate nicotianamine, ethylene glycol-bis(β-aminoethyl ether)-N,N,N Be selected from',N'-tetraacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, iminodiacetic acid, nitrilotria or diethylenetriaminepentaacetic acid I can.

The present invention consisting of the above-described characteristics, in preparing a maleic anhydride-modified fatty acid polyamide resin, by adding a Group 4 element-based complex compound obtained by a specific method at a certain ratio, can significantly improve the elongation characteristics of the paint. have.

In addition, it is possible to maintain excellent wear resistance and weather resistance, which are general characteristics required in paints, as well as increase peel strength and improve retroreflectivity through improvement of adhesive strength.

1 is a process chart showing an example of a manufacturing process of a fusion-type lane tape for road marking according to the present invention,
2 is a flow chart showing a working process in which a fusion-type lane tape is constructed.

Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the accompanying drawings, but specific structures and functions thereof are not limited to the embodiments described in the present specification since they represent one configuration example.

First, the fusion-type paint according to the present invention is composed of a modified polyamide resin, an extender pigment, a colorant, a wax, and a heat stabilizer.

The modified polyamide resin is prepared by condensation polymerization of ethylenediamine in a dimer acid made of one or more fatty acids selected from the group consisting of palm oil, tung oil, soybean oil and perm oil to prepare a polyamide, and 100 parts by weight of the polyamide After graft copolymerization by adding 3 to 10 parts by weight of maleic anhydride, 1 to 2 parts by weight of a Group 4 element-based complex compound is added and mixed.

In addition, in the step of preparing the polyamide, the polyamide resin is preferably 50 to 90 parts by weight of dimer acid and 5 to 30 parts by weight of ethylenediamine based on the total weight.

Here, when the amount of dimer acid exceeds 90 parts by weight, unreacted dimer acid may be present during synthesis, causing a reversible reaction after completion of the reaction, resulting in deterioration of physical properties or may become waxy. In addition, if it is less than 50 parts by weight, it is not preferable because the decrease in physical properties due to the generation of monomolecular polyamide or residual phenomena of ethylenediamine may occur, and ethylenediamine is not preferred. It is set to 5 to 30 parts by weight.

3 to 10 parts by weight of maleic anhydride is used in 100 parts by weight of the polyamide resin prepared in the above step, and this is grafted at a high temperature of 20 to 250°C using a double screw extruder.

At this time, as the content of maleic anhydride increases, the crosslinking density increases, so that the melting point of the resin increases, and polyamide resins having various crosslinking densities can be prepared according to temperature and pressure. Then, 1 to 2 parts by weight of a Group 4 element-based complex compound is added to the polyamide resin grafted with maleic anhydride, and homogeneously mixed to obtain a modified polyamide resin.

According to another preferred embodiment of the present invention, the group 4 element-based complex compound is a titanium ion source, a zirconium ion source, a hafnium ion source, a rudphonium ion source, or a combination thereof reacting with a first chelating compound in a first reaction. And a titanium, zirconia, hafnia, or rudphonium-based complex obtained by reacting with a secondary chelating compound in a subsequent secondary reaction.

In addition, the titanium ion source, zirconium ion source, hafnium ion source, or rudphonium ion source is preferably titanium oxide, zirconium oxide, hafnium oxide, or rudphonium oxide, respectively.

According to another preferred embodiment of the present invention, each of the chelating compounds is ethylenediaminetetraacetic acid (EDTA), glycinate, ethylene diamine, aspartic acid, amino acid glycine, aminopolycarboxylate nicotianamine, ethylene glycol- Bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid ( DOTA), iminodiacetic acid (IDA), nitrilotria or diethylenetriaminepentaacetic acid (DTPA) may be at least one selected from, and most preferably, ethylenediaminetetraacetic acid (EDTA), glycinate, or ethylene It is a diamine.

According to another embodiment of the present invention, the Group 4 element-based complex is specifically reacted with a zirconium ion source or a hafnium ion source or a combination thereof with ethylenediaminetetraacetic acid (EDTA) in a first reaction, and subsequent 2 It is a zirconia, or hafnia-based complex compound obtained by reacting with ethylene diamine in a secondary reaction.

According to another embodiment of the present invention, the EDTA used in the first reaction may be EDTA disodium salt dihydrate, and when it is used, the chelate reaction can be effectively performed, so it is preferable.

Although not particularly limited thereto, according to another preferred embodiment of the present invention, the Group 4 element-based complex compound according to the present invention may be an aqueous solution, and in particular, the aqueous solution does not have an organic solvent and has a pH of 2 to 7 It may be a solution to have.

In addition, the present invention provides a fusion-type paint for road signs comprising the polyamide resin prepared by the above method.

The specific composition ratio of the paint in the present invention includes 15 to 30 parts by weight of a polyamide resin, 30 to 40 parts by weight of an extender pigment, 2 to 15 parts by weight of a coloring material, 1 to 2 parts by weight of a wax, and 0.5 to 1.5 parts by weight of a heat stabilizer. Can include.

The method for preparing the polyamide resin according to the present invention will be described in more detail as follows. That is, polyamide is prepared by condensation polymerization of ethylene diamine with dimer acid containing fatty acids of palm oil, tung oil, soybean oil, and castor oil. Here, 5 to 30 parts by weight of ethylene diamine are reacted with 50 to 90 parts by weight of dimer acid containing fatty acids of palm oil, tung oil, soybean oil, and castor oil.

The selected fatty acid has a difference in the content of each unsaturated fatty acid (C11 ~ C22), and accordingly, the difference in molecular weight and the crosslinking density are different during polymerization. Depending on the type of fatty acid of palm oil, tung oil, soybean oil, castor oil, 50 to 90 parts by weight are used, and the value of ethylene diamine is set at 5 to 30 parts by weight according to the mole fraction (mole fraction = number of moles of dimer acid / number of moles of ethylene diamine).

Then, by adding 3 to 10 parts by weight of maleic anhydride to 100 parts by weight of the prepared polyamide resin, graft copolymerization at a temperature of 20 to 250°C, preferably a zirconium ion source or a hafnium ion source, or a combination thereof 1 Modified polyamide resin by reacting with ethylenediaminetetraacetic acid (EDTA) in a secondary reaction, and adding zirconia or hafnia-based complex compound obtained by reacting with ethylene diamine in a subsequent secondary reaction and mixing homogeneously To manufacture.

Next, a method for producing a fusion-type paint from the polyamide resin prepared according to the present invention will be described in more detail.

That is, 15 to 30 parts by weight of the modified polyamide resin, 30 to 40 parts by weight of extender pigments (calcium carbonate, dolomite), 2 to 15 parts by weight of colorants (white, yellow, blue), 1 to 2 parts by weight of wax, heat 0.5 to 15 parts by weight of a stabilizer is mixed to prepare a paint.

At this time, the extender pigments calcium carbonate (Omiya 10-CN Co., Ltd.) and Dolomite (products such as Ilshin Materials D-2460, etc.) show the effect of increasing the adhesion to the base surface and improving the abrasion resistance. Determine within the range of increasing viscosity. The colorant is selected by selecting a pigment suitable for the specified color and heat resistance (Dupon Ti-pure TiO2 R-900, Wooshin Co., Ltd. Yellow 1011, Blue 1-6B, etc.), and its content is determined according to the degree of coloring.

The wax is PE wax (products such as SINOPLAS Q-112, Inc.) and the melting point of 95 to 105℃ is used to improve water repellency and wear resistance by floating on the surface of the paint. When using less than 1 part by weight There is an increase in product viscosity and a decrease in abrasion resistance, and when the product is used in excess of 2 parts by weight, phase separation of the paint in the melting tank occurs due to a decrease in the product viscosity, and a certain coating quality cannot be obtained.

Thermal stabilizers (C&A Co., Ltd. CINANOX, etc.) are used to prevent color change from occurring when the paint is dissolved at 180 to 230℃, and when using less than 0.5 parts by weight, there is some change in color due to heat, 1.5 weight When used in excess of parts, the increase in stability is insignificant and tends to act as an impurity in the paint, which is not preferable.

Hereinafter, embodiments of the present invention will be described in detail, but it is a matter of course that the scope of the present invention is not limited to these embodiments.

Example 1

9 parts by weight of ethylene diamine (EDA) was added to 90 parts by weight of a fatty acid consisting of 52 parts by weight of castor oil, 17 parts by weight of copper oil, 17 parts by weight of soybean oil, and 4 parts by weight of palm oil, and a radical initiator (PERHEXA25B-40; Dongsung Co., Ltd.) 0.1 Part by weight was added and reacted at about 150 to 200°C, and the reaction was terminated when the acid value was 3 or less, and vacuum dehydration was performed to remove unreacted EDA.

Then, 5 parts by weight of maleic anhydride (product of Xiamen D.T. Co., Ltd.) was added to 100 parts by weight of the polyamide resin prepared above, and graft-copolymerized under a temperature of 200°C and a pressure of 500 kgf/㎠, and zirconium oxide was separately A zirconia-based complex obtained by reacting with ethylenediaminetetraacetic acid (EDTA) in the first reaction and reacting with ethylene diamine in the subsequent second reaction was obtained, and 1.5 parts by weight of the obtained zirconia-based complex was added to the graft copolymer and homogenized. By mixing, a modified polyamide resin was prepared.

Example 2

Except for using hafnium oxide instead of zirconium oxide in Example 1, a modified polyamide resin was prepared in the same manner as in Example 1.

Example 3

30 parts by weight of the modified polyamide resin prepared in Example 1, 37 parts by weight of extender pigments (calcium carbonate, dolomite), 10 parts by weight of colorant (white), 2 parts by weight of wax, and 1 part by weight of a heat stabilizer were mixed to prepare a paint. Was prepared.

Example 4

A paint was prepared in the same manner as in Example 3, except that the polyamide resin in Example 3 was used as the modified polyamide resin prepared in Example 2.

Comparative Example 1

A modified polyamide resin was prepared in the same manner as in Example 1, except that the step of adding the zirconia-based complex compound was omitted in Example 1 above.

Comparative Example 2

30 parts by weight of the modified polyamide resin prepared in Comparative Example 1, 37 parts by weight of extender pigment (calcium carbonate, dolomite), 10 parts by weight of colorant (white), 2 parts by weight of wax, and 1 part by weight of heat stabilizer were mixed to prepare a paint. Was prepared.

Comparative Examples 3 to 4

Comparative Examples 3 to 4 each prepared a paint by mixing 30 parts by weight of the following resin, 37 parts by weight of extender pigments (calcium carbonate, dolomite), 10 parts by weight of colorant (white), 2 parts by weight of wax, and 1 part by weight of a heat stabilizer. I did.

Comparative Example 3 : Polyamide resin, high-performance fusion-type road sign paint / conversation paint

Comparative Example 4 : Petroleum resin, fusion-type road sign paint / conversation paint

Comparative Example 5 : Acrylic emulsion, KS M 6080 2 types/Daehwa paint

Experimental example

The physical properties of the paints prepared in the above Examples and Comparative Examples were evaluated in the following manner, and are shown in Table 1.

1) Adhesion strength: According to ASTM D 1005, two aluminum specimens were attached with a paint and then completely cured, and the test was performed with shear adhesion by tension.

2) Tensile strength: The paint was completely dry-hardened according to ASTM D 638 to make a 3.2 mm-thick test piece and then measured with a universal testing machine.

3) Elongation: Elongation in a tensile test was measured according to ASTM D 638.

4) Wear resistance: Abrasion resistance was evaluated according to the method of KS M 6080;2014.

5) Impact strength: After drying and curing the paint completely according to ASTM D 256, a test piece having a thickness of 3.2 mm was made, and then tested with an Izod impact tester, as shown in Table 1 below.

Item unit Example 3 Example 4 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Adhesive strength N/㎡ 38 41 40 18 19 16 The tensile strength N/㎟ 7.6 7.3 7.5 3 Not measurable Not measurable Elongation % 117 116 62 38 45 67 Wear resistance mg 80 79 80 150 230 Not measurable Impact strength kgf.cm/cm 3.8 3.9 3.6 2.1 2.5 2.0

The coatings of Examples 3 and 4 using the modified polyamide resin prepared by grafting maleic anhydride to the polyamide resin according to the present invention and adding a specific Group 4 atom-based complex compound were compared as shown in Table 1 above. Compared with Examples 3 to 5, it is excellent in adhesive strength, tensile strength, abrasion resistance, and impact strength, and exhibits substantially similar physical properties to Comparative Example 2, but exhibits remarkably high elongation.

Meanwhile, as shown in FIG. 1, the fusion-type paint prepared as described above may be manufactured into a tape of a certain standard through a predetermined process. That is, the fusion-type paint is supplied from the paint dissolution tank 101 to the drum 102 and is cooled by a release agent sprayed through the release agent nozzle 103 to form a uniform thickness.

At this time, while the glass beads supplied from the glass bead sprayer 104 are evenly sprayed onto the surface of the tape, which is less cured, it is pressed while passing between the bead pressing rollers 105, and then transferred through the conveyor 106. Hardening takes place gradually in the process.

Thereafter, the tape is wound up to a predetermined length by a winding machine 108 installed at the rear end of the conveyor 106 and cut into a predetermined length using a cutting machine 107.

As shown in FIG. 2, in the case of installing the tape, after cleanly removing dust and foreign substances from the road surface (step S311), mark the part to which the lane tape will be attached in advance, and apply a primer thereon Apply and dry (step S312).

At this time, as the primer, a conventional fusion primer (acrylic resin: 60 parts by weight, toluene: 40 parts by weight) may be used.

Subsequently, the lane tape is cut to a set width in accordance with the corresponding display area (step S313), and the lane tape is arranged on the road surface (step S314), and then heated and fused using a surface combustion burner (S315).

In this way, when the construction work on the lane tape is completed, it is finally checked whether the lane tape is adhered to each other, and finishing work such as re-compression and sealing work is performed on the part determined to be incomplete (step S316), and then it is finished.

The configuration or construction process of the lane tape as described above is almost the same as the example that is already being carried out, and it can be constructed in the same way not only for vehicles and pedestrian guidance lines displayed on the road, but also for signs and characters, and the lanes are painted. It is natural that it can be applied to new roads as well as existing roads.

As described above, according to the fusion-type lane tape for road marking according to the present invention, in preparing a maleic anhydride-modified fatty acid polyamide resin, a group 4 element-based complex obtained by a specific method is added at a certain ratio, The elongation property can be remarkably improved.

In addition, it is possible to maintain excellent wear resistance and weather resistance, which are general characteristics required in paints, as well as increase peel strength and improve retroreflectivity through improvement of adhesive strength.

The technical task of the present invention is achieved by the technical configuration as described above, and although it has been described by the limited embodiments and drawings, the present invention is not limited thereto, and the present invention is by those of ordinary skill in the art. It goes without saying that various modifications and variations are possible within the scope of the technical idea of and the claims to be described below.

101: paint dissolution tank 102: drum
103: release agent nozzle 104: glass bead sprayer
105: bead pressing roller 106: conveyor
107: cutting machine 108: winding machine

Claims (1)

To prepare a polyamide by condensation polymerization of ethylendiamine in a dimer acid prepared from one or more fatty acids selected from the group consisting of palm oil, tung oil, soybean oil and castor oil,
After adding 5 parts by weight of maleic anhydride to 100 parts by weight of the polyamide and performing graft copolymerization at 200°C and under 500 kgf/cm 2 pressure,
Zirconium oxide was first reacted with ethylenediaminetetraacetic acid (EDTA) and then 1.5 parts by weight of a zirconia-based complex compound prepared by reacting with ethylenediamine in a subsequent second reaction was added to the graft copolymer to prepare a modified polyamide resin. , 30 parts by weight of the modified polyamide resin, 37 parts by weight of an extender pigment composed of calcium carbonate dolomite, etc., 10 parts by weight of a colorant, 2 parts by weight of wax, and 1 part by weight of a heat stabilizer are mixed to prepare a paint,
A fusion-type lane tape for road marking manufactured by supplying the paint to the surface of a drum and cooling it to maintain a constant thickness, and at the same time, by spraying and pressing a glass bead on the surface and then curing it.

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