KR20170069531A - Road Sign Marking Composition Improved Visibility - Google Patents

Abstract

The present invention is to provide a road marking composition which exhibits excellent visibility at night or in bad weather, has excellent strength equivalent to or better than that of a road surface composition for roads, has excellent adhesion and adhesion, The present invention relates to a composition for road surface marking that is excellent in elongation and shearing strength and is free from yellowing due to ultraviolet rays and has a very small thermal expansion coefficient to suppress cracking and tearing due to temperature contraction. Wherein the composition comprises a main portion and a curing agent portion; The subject part may be formed by adding a catalyst selected from a metal catalyst or an amine catalyst, a defoaming agent, a coupling agent, an antifoaming agent, an antifoaming agent or a coupling agent to any one selected from an aliphatic polyol or an aliphatic polyetheramine or a mixture of an aliphatic polyol and an aliphatic polyether amine , A phosphorescent pigment, a dispersant, and a flow control agent; The curing agent part is an aliphatic isocyante having an NCO reactor and is composed of a prepolymer having an NCO content of 15 to 30% by synthesis of an aliphatic isocyanate alone or an aliphatic isocyanate and an aliphatic polyol; The mixing ratio of the main portion and the curing agent portion is 100: 50 to 200 by weight.

Description

BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates to a road sign marking composition improved visibility,

TECHNICAL FIELD The present invention relates to a paint composition for displaying a lane or the like on a road surface of a road, and more particularly, to a paint composition for use in a polyol mixture as a subject and transparent The present invention relates to a composition for road surface marking which is capable of improving the visibility in the event of bad weather such as nighttime or rainy weather by adding a phosphorescent pigment to a binder and adding an organic electroluminescent (EL) light emitting material.

Generally, on a packed road, a road marking for inducing a lane of a certain width is installed in order to guide the direction of the road and maintain the interval between the cars. There are various types of road markings on the road, such as information on the speed limit and the destination of the destination, which are directly applied on the road surface of the road, and may be displayed as letters or figures. The lane marking the driving direction of the vehicle and the safety And the like, and various road marking paints used therein are developed and used in various kinds.

The paint composition for road marking, which is commonly used, is hardly recognized on a non-illuminated section road, and can be recognized only to the distance that light from the headlamp reaches. In the case of automobiles, the irradiation length of the headlights is only 50 to 60 m in the downward direction and 90 to 100 m in the upward direction, and it is common to drive the vehicle in a downward light state due to the inconvenience of operation of the headlight. In the case of the section, traffic lights are frequently generated due to inconsistency with the direction of headlights.

Conventionally, a retroreflector, a coloring pigment, a phosphorescent pigment and the like are mixed in a road surface display paint to improve the visibility of a driver and a pedestrian in the nighttime or in bad weather.

However, such a conventional coating composition for road marking has a problem in that it causes temperature shrinkage, yellowing due to ultraviolet rays, brittle fracture due to vehicle load, cracking and tearing caused thereby, and visibility of road surface marking is remarkably lowered There is a problem.

Registration No. 10-1325529 (registered on October 30, 2013) Registration No. 10-1311704 (Registered on September 17, 2013) Japanese Unexamined Patent Publication No. 2003-277341 (published on October 22, 2003)

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and it is an object of the present invention to provide a road marking composition which exhibits excellent visibility at night or in bad weather, Which is excellent in adhesion to phosphorescent pigments, has excellent elongation and shear strength, has no yellowing due to ultraviolet rays, and has a very small thermal expansion coefficient, so that cracks and tears due to temperature shrinkage can be suppressed. And to provide a composition for display.

According to an aspect of the present invention, there is provided a road surface composition for road surface display comprising a main portion and a curing agent portion; The subject part may be formed by adding a catalyst selected from a metal catalyst or an amine catalyst, a defoaming agent, a coupling agent, an antifoaming agent, an antifoaming agent or a coupling agent to any one selected from an aliphatic polyol or an aliphatic polyetheramine or a mixture of an aliphatic polyol and an aliphatic polyether amine , A phosphorescent pigment, a dispersant, and a flow control agent; The curing agent part is an aliphatic isocyante having an NCO reactor and is composed of a prepolymer having an NCO content of 15 to 30% by synthesis of an aliphatic isocyanate alone or an aliphatic isocyanate and an aliphatic polyol; The mixing ratio of the main portion and the curing agent portion is 100: 50 to 200 by weight.

The composition for road surface display of the present invention is characterized in that the binder material composed of the main part and the curing agent has high transparency, suppresses yellowing due to ultraviolet rays, is excellent in strength and adhesiveness and therefore does not crack or tear, The visibility is remarkably improved by the light emitting body, thereby providing a great effect in safe operation.

Also, since the composition for road surface display according to the present invention has a behavior similar to the dynamic modulus of a general asphalt pavement, when the expansion and contraction of the asphalt pavement are repeatedly generated according to the temperature, the road marking composition is similar to the asphalt pavement Expansion and contraction can be prevented, and cracks and desorption due to temperature changes can be prevented.

1 is a cross-sectional view illustrating a road surface composition according to an embodiment of the present invention applied to a road pavement.
2 is a cross-sectional view illustrating a road surface composition according to another embodiment of the present invention applied to a road pavement.
FIG. 3 is a photograph of illuminance measured in a state that the road marking composition according to the present invention is applied to a road pavement.

The road surface display composition according to the present invention is constituted by mixing a phosphorescent pigment with a two-component type transparent binder composed of a main portion containing a polyol mixture and a curing agent portion containing isocyanate and emit light.

The road surface marking composition according to an embodiment of the present invention may be prepared by adding a metal catalyst or an amine to an aliphatic polyol or an aliphatic polyetheramine or a mixture of an aliphatic polyol and an aliphatic polyether amine, A main part made of a catalyst selected from a catalyst, a defoaming agent, a coupling agent, a phosphorescent pigment, a dispersant, and a flow control agent; An aliphatic isocyante having an NCO reactor and composed of a prepolymer having an NCO content of 15 to 30% by synthesizing an aliphatic isocyanate alone or an aliphatic isocyanate with an aliphatic polyol . The mixing ratio of the main portion and the curing agent portion is 100: 50 to 200 by weight.

The curing agent is an aliphatic isocyante having an NCO reactor and may be composed of a prepolymer having an NCO content of 15 to 30% by synthesizing an aliphatic isocyanate alone or an aliphatic isocyanate with an aliphatic polyol. In the present invention, the content of NCO is expressed as a percentage (% by weight) of the weight of NCO contained in the isocyanate compound, and can be measured according to KS M 5969 (test method for isocyanate group content in urethane intermediate or prepolymer).

The aliphatic isocyanate is selected from among IPDI (Isophrone Diisocyanate), HDI (Hexamethylene Diisocyanate) and HMDI (Methylene Dicyclohexyl Diisocyanate).

The NCO% Viscosity (25 ℃) Specific gravity (20 ℃) Molecular Weight Number of functional groups equivalent weight IPDI C ₁₂ H ₁₈ N ₂ O ₂ 37.8 5 to 15 1.06 222.29 2 111.14 HDI OCN (CH ₂ ) ₆ NCO 49.9 3 1.05 168.19 2 84.1 HMDI C ₁₅ H22N ₂ O ₂ 32 30 1.07 262.35 2 131.18

Isocyanate is largely divided into aromatic isocyanate and aliphatic isocyanate. It is preferable to use non-yellowing aliphatic isocyanate which is transparent and has little influence of yellowing for continuous implementation of transparency. Prepolymer Isocyanate Using Aliphatic Isocyanate It is also preferable to use an aliphatic isocyanate prepolymer free from ultraviolet rays by synthesis of an aliphatic isocyanate and an aliphatic polyol.

When Aromatic Isocyanate is used, Aromatic Ring (benzene ring) part forms Monoquione Imide (quinone ring) by radical reaction by ultraviolet rays and acts as a chromophore, so that the color turns yellow and the transparency Fall off.

The subject part may be an aliphatic polyol having a weight average molecular weight of 100 to 3000 and a functional group of 2 to 10 or an aliphatic polyetheramine having a weight average molecular weight of 200 to 5000 and having 2 to 3 functional groups, 0.01 to 3% by weight of a catalyst, 0.01 to 2% by weight of a defoaming agent, 0.1 to 5% by weight of a coupling agent, 1 to 20% by weight of a phosphorescent pigment, 0.1 to 3% by weight of a dispersing agent, and 1 to 10% .

The aliphatic polyol is a raw material having an OH reactor as a polyurethane subject, and only an aliphatic polyol is used without using an aromatic polyol for color development, colorlessness and transparency expression of a phosphorescent pigment. Two or more polyols differing in molecular weight and number of functional groups can be used to realize properties.

The aliphatic polyol is composed of any one selected from a mixture of an aliphatic polyetherpolyol or a biomass-containing polyol or an aliphatic polyether polyol and a biomass-containing polyol.

The bio-polyol may be a vegetable natural polyol such as castor oil, castor oil, soybean oil, rapeseed oil, cottonseed oil, Natural polyols prepared by epoxidation, ring opening and alkoxylation while oxidizing vegetable oil such as palm oil, sunflower oil and the like with peroxycarboxylic acid or carboxylic acid may be used. The bio-polyol has a function of improving the elasticity of the composition for road surface display according to the present invention, while having an environment-friendly performance.

The aliphatic polyetheramine is a polyurea subject and is a raw material having an NH ₃ reactor. When aliphatic polyether amines are used, aliphatic polyether amines are used for transparency expression as in the case of the polyols described above, and physical properties are realized by using two or more aliphatic polyether amines having single or different molecular weights and functional groups.

In the case of aliphatic polyether amines, aliphatic polyether amines having a weight average molecular weight of 200 to 5000 and 2 to 3 functional groups are used.

Or an aliphatic polyol (polyurethane subject) and an aliphatic polyether amine (polyurea subject), which are fast in reaction, are mixed in the main part to realize various properties by polyurethaneurea bonding and a composition for transparency road surface display can do.

The reaction mechanism between polyurethane and polyurea is as follows.

Isocyanate (-NCO) + polyol (-OH) - > urethane (-NHCOO-)

Isocyanate (-NCO) + amine (-NH ₃₎ → urea (-NHCONH-)

The catalyst is selected from a metal catalyst or an amine catalyst as a gelling catalyst for promoting the resinization reaction between a polyol and an isocyanate. As the metal catalyst, DBTL (Dibutyltin dilaurate) or Stannous octoate may be used. As the amine catalyst, at least one of TEDA (triethylene diamine), DMEA (Dimethyl ethanolamine), TMBDA (Tetramethyl butane diamime), DM C HA (Dimethyl cyclohexyl amime) and TEA (Triethyl amine) can be used.

The defoaming agent acts to remove air bubbles generated by the reaction or bubbles generated by mixing by lowering the surface tension due to the defoaming agent. The function of the antifoaming agent is classified into three types of action mechanisms, namely, papermaking, defoaming, and defoaming. The generic term of defoaming agent, defoaming agent and defoaming agent is defined as antifoaming agent. It means that the foam penetrates into the foam from the air side and unifies or destroys the foam, and the foam penetrates into the foam from the liquid side to unite or break the foam to make the foam impossible, Means that it penetrates into the interface of the bubble and coalesces the bubble.

Examples of the defoaming agent include silicone defoaming agents, modified silicone defoaming agents, silica silicone defoaming agents, acrylic polymer defoaming agents, fluorine defoaming agents, ether defoaming agents, ester defoaming agents and alkyl oxide fatty acids.

The coupling agent has two or more reactors in the molecule, and has a reactor chemically bound to the organic material and a reactor chemically coupled to the inorganic material. Therefore, it plays a role of connecting the organic materials, thereby improving the adhesion between the organic polyurethane and the bottom pavement surface containing the aggregate, which is an inorganic interfacial material. Through this, the mechanical strength, chemical resistance, abrasion resistance and scratch resistance .

As the coupling agent, a double silane coupling agent such as a silane coupling agent, a phosphorous coupling agent, a titanate coupling agent, and a chromium coupling agent may be used. Depending on the kind of the organic functional group, an epoxy silane, an aminosilane, Methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, Examples of the chlorosilane include dimethyldichlorosilane, methyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, trichlorosilane, trimethylchlorosilane, silicon tetrachloride, and vinyltrichlorosilane.

The phosphorescent pigment (phosphorescent pigment) may be a known phosphorescent pigment as an inorganic substance used for color development of a lane. The phosphorescent pigment is a pigment having a property of absorbing and storing light and emits and emitting light. The pigment is composed of an emulsified zinc-based (ZnS: Cu) pigment (yellow-green color) containing a trace amount of copper, strontium activated with europium (SrAl2O4: Eu, Dy) and the like can be used.

The dispersing agent is more precisely referred to as a wetting dispersing agent and is used for effectively dispersing the phosphorescent pigment in the main portion. The stability of the pigment dispersion through the dispersing agent in the paint is essential to ensure the uniformity of the quality. The physical properties such as storage stability, application properties, and final coating properties .

The coating material having good pigment dispersion has excellent coloring power, hiding power, smoothness of the film, leveling and gloss, and prevents color separation and color stain.

As the non-aqueous wetting and dispersing agent, a relatively high molecular weight anionic compound, a cationic compound and an electrically neutral compound are frequently used. Examples thereof include aliphatic carboxylic acids and salts, higher alcohol sulfate esters, alkyl sulfonic acid salts, Polyesters, polyesters, polyester-esters, polyamines of polymeric polyestercarboxylic acids, aliphatic amine salts, quaternary ammonium salts, long-chain polyaminoamides and their phosphates, long-chain polyaminoamides and polymers of polyester A neutral salt and the like can be used.

Examples of the wetting and dispersing agent for water include anionic and nonionic ones such as polyacrylic sodium, compounds of styrene-maleic anhydride (or olefin) copolymer, sodium alkylnaphthalenesulfonate-formalin condensate, Sodium sulfonate, polyethylene glycol phenyl ether, polyethylene glycol high alkyl, ether dialkyl dulfo succinate, sorbitan aliphatic ethylene oxide adduct, and the like.

The flow control agent is an additive for controlling thixotropic or flowability by weak hydrogen bonding or ionic bonding. It is possible to adjust the spreadability of the coating composition by adjusting the flow property when the road marking composition (coating material) is applied, To prevent separation phenomenon such as prevention of precipitation of phosphorescent pigment.

The flow control agent may be classified as an aqueous flow control agent and an oil-based flow control agent, and may be classified as an amine group or as an adsorptive group and a compatibility group.

Examples of the flow control agent include silica powder, calcium carbonate, nano-clay, and modified urea-based polymers.

Meanwhile, the composition for road surface display of the present invention can improve the visibility due to the luminescent phenomenon of the phosphorescent pigment, but in order to compensate the material limit of the phosphorescent pigment, as shown in Fig. 1, (EL) light emitting element 3 is embedded in a composition for road surface display when the organic electroluminescent element 3 is applied to a package and electric power is connected to the organic EL element 3, The visibility can be further improved together with the phosphorescent pigment 2 by making it emit light by electricity.

The organic electroluminescent material 3 may be an elongated strip or a plate as shown in FIG. 1, but may be a wire as shown in FIG.

The road surface display structure shown in another embodiment of FIG. 2 cuts a groove 4 for inserting a wire-shaped organic electroluminescent light emitting element 3 into a road, and then cleanses and arranges the inside of the groove 4 to remove foreign matter The interior of the groove 4 is treated with the road surface marking composition 1 of the present invention and then the organic electroluminescent material 3 is applied to the interior of the groove 4, do.

Example 1

division Product Name input Average equivalent Number of functional groups Percent (wt%) One IPDI 75 111.14 2 75 2 GP-1000 25 334 3 25

Table 2 shows the curing agent part. The curing agent part is an IPDI product of Germany Evonik, which is an aliphatic isocyanate having an NCO content of 37.7% and a viscosity of 5 to 15 cps at 25 ° C and a product (GP-1000) of KPX Chemical Co., A prepolymer product synthesizing an aliphatic polyol having three functional groups with an average molecular weight of 1000 was used, and the NCO content of the prepolymer was 24.98%.

division Product Name input Average equivalent Percent (wt%) One GP-400 85 140 70.42 2 GP-3000 20 334 17.61 3 DBTL 0.5 0.44 4 Defoamer 0.1 0.09 5 Silane coupling agent 2 1.76 6 Phosphorescent pigment 7 6.16 7 Dispersant One 0.88 8 Flow control agent 3 2.64 Sum - 113.6 100

In Table 3, the aliphatic polyol of the subject part was mixed with GP-400 aliphatic polyol and GP-3000 aliphatic polyol of KPX Chemical Co., Ltd. for adjusting the physical properties. The GP-400 aliphatic polyol is a three-functional product having a number average molecular weight of 420 and the GP-3000 aliphatic polyol is a three-functional product having a number average molecular weight of 1,000.

The results of physical properties of the composition for road surface display of Example 1 and Comparative Example 1 (5 types of MMA lacquer paint), which were prepared by mixing 100 parts by weight of the curing agent and the main portion in the weight ratio, are shown in Table 4 below.

Test Items Comparative Example 1 Example 1 Test Methods Hardness (Shore D) 74 68 KS M ISO 868 Tensile strength (kgf / cm2) 150 235 KS M 6518 Elongation (%) 5 138 KS M 6518 Tear strength (kgf / cm) 37 144 KS M 6518 Maximum load displacement (mm) 0.46 33.43 KS M 6518

As shown in Table 4, it was confirmed that the tensile strength, elongation, and tear strength of the composition for road surface display of the present invention were remarkably increased compared to Comparative Example 1 (MMA: Methyl Methacrylate).

Further, since the composition for road surface display of the present invention additionally comprises an organic electroluminescent material, when power is applied to the organic electroluminescent material at night, the visible display can be improved by emitting light as shown in FIG. In addition, the composition for road surface display of the present invention has an advantage that transparency is high so that light of the organic electroluminescent material is well emitted to the outside and yellowing phenomenon by ultraviolet rays does not occur.

As described above, the composition for road surface display of the present invention has a high transparency of the binder material composed of the main portion and the curing agent, suppresses yellowing due to ultraviolet rays, is excellent in strength and adhesiveness and does not crack or tear, EL) light-emitting body, thereby providing a great effect on safe operation.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the present invention as defined by the appended claims. And it is to be understood that such modified embodiments belong to the scope of protection of the present invention defined by the appended claims.

1: composition for road surface display 2: phosphorescent pigment
3: Organic electroluminescent (EL) emitter

Claims (10)

A topical portion and a hardener portion;
The subject part may be formed by adding a catalyst selected from a metal catalyst or an amine catalyst, a defoaming agent, a coupling agent, an antifoaming agent, an antifoaming agent or a coupling agent to any one selected from an aliphatic polyol or an aliphatic polyetheramine or a mixture of an aliphatic polyol and an aliphatic polyether amine , A phosphorescent pigment, a dispersant, and a flow control agent;
The curing agent part is an aliphatic isocyante having an NCO reactor and is composed of a prepolymer having an NCO content of 15 to 30% by synthesis of an aliphatic isocyanate alone or an aliphatic isocyanate and an aliphatic polyol;
Wherein the mixing ratio of the main portion to the curing agent is 100: 50 to 200 by weight. The photosensitive resin composition according to claim 1, wherein the main portion comprises 59 to 97 wt% of an aliphatic polyol or aliphatic polyetheramine, 0.01 to 3 wt% of a catalyst, 0.01 to 2 wt% of an antifoamer, 0.1 to 5 wt% of a coupling agent, 0.1 to 3 wt% of a dispersant, and 1 to 10 wt% of a flow control agent. The composition according to claim 1 or 2, wherein when the aliphatic polyol is used in the main portion, the aliphatic polyol has a weight average molecular weight of 100 to 3000 and a functional group of 2 to 10 . The method according to claim 1 or 2, wherein when the aliphatic polyether amine is used in the main portion, the aliphatic polyether amine has a weight average molecular weight of 200 to 5000 and a functional group of 2 to 3, Composition for road surface marking. The method according to claim 1 or 2, wherein the aliphatic polyol is selected from a mixture of an aliphatic polyetherpolyol or a biomass-containing polyol or an aliphatic polyether polyol and a biomass-containing polyol By weight based on the total weight of the composition. The composition according to claim 5, wherein the biomass-containing polyol is selected from the group consisting of castor oil and soybean oil based polyol. The composition according to claim 1 or 2, wherein the catalyst is selected from DBTL (Dibutyltin dilaurate) and TEDA (triethylene diamine). The method according to claim 1 or 2, wherein the aliphatic isocyanate of the curing agent part is selected from IPDI (Isophrone Diisocyanate), HDI (Hexamethylene Diisocyanate) and HMDI (Methylene Dicyclohexyl Diisocyanate) / RTI > The visibility display device according to claim 1 or 2, further comprising an organic electroluminescent (EL) emitter which is embedded in the road marking composition and emits electricity when the road marking composition is applied to the road pavement A composition for improved road surface marking. A topical portion and a hardener portion;
The subject part may be an aliphatic polyol having a weight average molecular weight of 100 to 3000 and a functional group of 2 to 10 or an aliphatic polyether amine or aliphatic polyether amine having a weight average molecular weight of 200 to 5000 and having 2 to 3 functional groups, 59 to 97% by weight of an aliphatic polyetheramine mixed with 0.01 to 3% by weight of a catalyst selected from a metal catalyst or an amine catalyst, 0.01 to 2% by weight of an antifoaming agent, 0.1 to 5% by weight of a coupling agent, 0.1 to 3% by weight of a dispersant, and 1 to 10% by weight of a flow control agent;
The curing agent part is an aliphatic isocyante having an NCO reactor and is composed of a prepolymer having an NCO content of 15 to 30% by synthesizing an aliphatic isocyanate alone or an aliphatic isocyanate with an aliphatic polyol, The aliphatic isocyanate is selected from among IPDI (Isophrone Diisocyanate), HDI (Hexamethylene Diisocyanate) and HMDI (Methylene Dicyclohexyl Diisocyanate);
Wherein the mixing ratio of the main portion to the curing agent is 100: 50 to 200 by weight.

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