KR102483195B1 - A road marking composition comprising polyurea and construction method using the same - Google Patents

Abstract

The present invention relates to a polyurea lane composition for road marking and a construction method using the same, and more particularly, by mixing an agent A containing isocyanate, an agent B containing a curing agent and functional additives, the protruding lane can be constructed using a coating composition.

Description

Composition for protruding lane markings containing polyurea paint and method for constructing protruding lanes using the same

The present invention relates to a composition for a protruding lane marking comprising a polyurea paint and a method of constructing a protruding lane using the same.

In general, in order to paint lanes or crosswalks, various paints with different construction methods, such as one-component, two-component, or fusion-type, are painted on the surface, and then glass microspheres (beads) are sprayed and finished. this is being done In such a method of painting lanes, etc., by spraying glass microspheres after painting, not only does it cause traffic congestion such as vehicle control until the product is dried when road traffic is opened, but also the gap between the glass microspheres and the paint layer is caused by vehicles after traffic is opened. Due to the lack of adhesion, the phenomenon of detaching quickly occurs, and the loss of retroreflective ability further adversely affects the brightness of the lane, making dangerous roads where the lanes are not visible, especially on rainy days.

In addition, among existing lane painting methods, the fusion method is a method of heating and applying in a powder state, which increases traffic control time in the summer season, and the two-component type (MMA, epoxy) painting work is hardened due to low air temperature in winter Time is slow, and durability is weakened due to discoloration or cracking after construction, resulting in low adhesive strength. In recent years, the rainy season (rainy season) has been getting longer and the amount of precipitation such as heavy rain has been increasing due to abnormal weather phenomena. As a result, the brightness of lanes is not sufficient and the risk of traffic accidents is increasing due to low visibility in rainy weather at night. to be.

Looking at the contents of the research and development of the road lane painting method and the patent application, Korean Patent Publication No. 1996-014174 contains 20-50% by weight of an acrylic acid ester-based monomer, 25-40% by weight of an aromatic vinyl-based monomer, and carboxylic acid vinyl ester. 60-80 parts by weight of acid value 40-60 mixed monomers including 25-40% by weight of monomers, 10-30 parts by weight of unsaturated carboxylic acid-based monomers, 10-30 parts by weight of unsaturated monomers having a hydroxyalkyl group, radical polymerization initiation catalyst 1 to 3 parts by weight and 5 to 50 parts by weight of a hydrophilic solvent are used to obtain a weight average molecular weight of 20,000-20,000- Disclosed is a water-soluble acrylic resin composition comprising 30-50 parts by weight of an acrylic resin prepared by secondary addition polymerization adjusted to 30,000, 0.1-5 parts by weight of a pH stabilizer, 0.5-5 parts by weight of a dispersant and 15-50 parts by weight of a pigment there is.

In addition, Korean Patent Publication No. 10-2014-0038787 discloses a one-component epoxy resin composition for paint without adding a curing agent, specifically, 5-15% by weight of epoxy resin, 25-35% by weight of trimethylolpropane, A composition comprising 30-40% by weight of musphthalic acid, 1-5% by weight of rosin and the balance soybean milk fatty acid is disclosed.

In addition, Korean Patent Laid-open Publication No. 1998-0021152 discloses that 10-90 parts by weight of an inorganic extender pigment having a size in the range of 5-250 mesh and having a Mohs hardness of 7 or more as an extender pigment and a synthetic resin in a solid amount of 4 -40 parts by weight and other additives are disclosed.

In addition, there are known products to improve abrasion resistance by using silica having a large particle size and hard as an extender pigment. The painted surface is easily cracked by the load and impact of a large truck, and glass microspheres added together to the composition to improve night visibility are often detached, so low visibility on dark nights, especially on rainy nights The risk of traffic accidents is very high, and supplementation is urgently needed.

On the other hand, polyfunctional amines are used as co-reactants with polyfunctional isocyanates in many applications. This reaction produces polyureas, which are noted as a class of polymers noted for their toughness, high strength and kinetic and high temperature performance. These reactions are usually carried out in specialized equipment due to the high reactivity of amines and isocyanates. Accordingly, its use is limited to traditional adhesive, coating and sealant type product applications.

Typical primary and secondary amines are highly reactive with various electrophiles and have very short gel times with little or no pot life. The reaction of primary amines with isocyanates is highly exothermic and produces strongly hydrogen-bonded dihydro-urea linkages. Strongly hydrogen-bonded groups have the disadvantage of increasing the viscosity of the product and further inhibiting the mobility and reactivity of the attached functional groups.

The usefulness of the amines of the present invention is based on an addition reaction between a polyisocyanate component and an isocyanate-reactive component, specifically a polyamine containing secondary amino groups. This reaction is known in principle from DE-OS 2,158,945 (Federation of Germany, 1973), but according to this publication, the reaction is conducted at relatively low temperatures rather than for the preparation of intermediate products which convert to heterocyclic final products at high temperatures. It is used for crosslinking of two-component coating compositions in

Bayer Corp. has recently produced a polyaspartic acid diester under the brand Desmophen ^™ . These secondary amines react with greater controllability with electrophiles than the corresponding primary amines. However, the addition reaction products of these amines with isocyanates further transform to form hydantoin ring structures, shrinking the coating and producing unwanted alcohol by-products.

U.S. Patent No. 5,126,170 describes secondary amines, referred to as "polyaspartic acid derivatives", which are formed by a Michael-type reaction of a primary amine with a maleic or fumaric acid ester Michael acceptor. The reaction can be explained by Reaction Scheme 1 below.

[Scheme 1]

In the above formula, R1, R2 and R3 are defined in the above literature.

These aspartic acid ester diesters react with isocyanates to form urea-diester bonds. This reaction can be explained by Reaction Scheme 2 below.

[Scheme 2]

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are defined in the above literature.

However, it has been reported that the urea-diester bond is unstable and cyclizes to hydantoin with alcohol extraction. The extracted alcohol causes problems by undergoing unwanted reactions with residual isocyanate groups in some series, such as isocyanate-terminated prepolymers. The dimensional change of the polymer upon formation of hydantoin is also an important problem. This reaction can be explained by Reaction Scheme 3 below.

[Scheme 3]

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are defined in the above literature.

In addition to U.S. Pat. Nos. 5,126,170, U.S. Pat. Nos. 5,236,741, 5,243,012, 5,412,056, 5,516,873 and 5,580,945, as specific end uses of the aforementioned aspartic acid ester diesters, are suitable for the manufacture of high-performance polyurethane or polyurea coatings. is described as

There is a high need for improved polyurea and polyurethane coatings with amine components that inhibit hydantoin formation. There is a distinct need for a liquid road marking composition that provides improved durability and retained reflectivity when dried or cured after surface application. Furthermore, it is advantageous to apply the markings in a wider range of climatic conditions than is possible with existing compositions.

There is also a need for marker compositions with improved cure profiles that ensure substrate wettability and fast track free times. Improvements must be made to prepare compositions that are substantially free of volatile organic components. Compositions of this type are typically used on roads, highways, parking lots and recreational trails to form lines, bars and markers for alleys, crosswalks, parking spaces, symbols and descriptions, and the like. They are typically applied by spray coating (ie painting) to the road surface. The treated road marking sheets or tapes have also been used to mark road pavement or traffic related surfaces.

Road marking strips or other shaped road markings may include reflective optical components attached to the road surface by a bonding agent. Current traffic coating systems typically use conventional 1.5 nD glass microspheres for increased retroreflectivity. These microspheres are typically flood coated onto wet markers immediately after coating. This provides the paint with improved retroreflective properties and also covers the top surface of the uncured or undried coating with a protective layer of microspheres. Since this protective layer is a layer of microspheres on the surface, the marker is more quickly exposed to traffic. This prevents the coating from migrating to the surface of the car tire. This is important for label application rates. The time after application until the material no longer migrated to the car tire was defined as the “track free” time. Shorter track free times increase sign efficiency by reducing or eliminating traffic jams by methods such as blocking roads or installing traffic control equipment to protect the signs.

US Patent No. 5,478,596 discloses a liquid road marking composition that solves several problems of alkyd and epoxy based road marking compositions. These road marking compositions are prepared from a two component polyurethane forming system with a first component (polyol) containing isocyanate-reactive groups and a second component containing isocyanate functional groups. Such compositions are disclosed to dry faster, have better weather resistance, and do not tarnish as easily as alkyd-based and epoxy-based compositions. However, the exemplified compositions require an aromatic isocyanate in combination with a polyol and catalyst. Any colorless or light colored aromatic polyisocyanate increases the reactivity, reduces the viscosity of the isocyanate component and provides a harder polyurethane. Aromatic isocyanates are particularly undesirable because the polyurethanes produced are prone to environmental degradation and discoloration. In addition, many low molecular weight aromatic isocyanates that reduce viscosity and change reactivity or film properties can potentially have significant inhalation hazards and toxicity related to vapor pressure. In addition, the use of a catalyst is undesirable because it can accelerate the degradation of polyurethane. To overcome the lack of aromatic isocyanates, aliphatic isocyanates can be used with polyols. However, in order to obtain a sufficient curing speed, a catalyst or an aromatic isocyanate must be used together with an aliphatic isocyanate.

Therefore, all of these properties (i.e., reducing environmental impact through formulations with low volatile organic content or substantially solvent-free formulations, improving the balance of coating fluidity during application and film formation to increase substrate wettability and track A liquid road marking composition that can simultaneously provide, in a single material, properties that rapidly cure to a free film, properties that increase the range of climatic conditions for coating, and properties that improve mark performance through increased durability and retained reflectivity. This is a situation in which a need is met by some degree of developed technology.

However, in particular, in the case of a protruding lane, it has a structure in which shear stress is applied innumerable times by automobile tires in operation and cracks are easily generated, and very excellent crack resistance is required.

In addition, compared to the case of non-protruding lanes, the surface of the protruding lane is damaged due to abrasion caused by friction with the tire, and as a result, the luminance value is lowered, which inevitably reduces visibility especially at night in rainy weather. .

Nonetheless, the technology for protruding lanes with sufficient crack resistance and luminance retention during sub-rainy weather has not been developed, and the industry has a great demand for this.

1. Korean Patent Registration No. 0180945 2. Korean Patent Registration No. 0316083 3. Korean Patent Publication No. 2005-0057864 4. U.S. Patent No. 5,126,170 5. U.S. Patent No. 5,126,170 6. US Patent No. 5,236,741 7. U.S. Patent No. 5,243,012 8. U.S. Patent No. 5,412,056 9. U.S. Patent No. 5,516,873 10. U.S. Patent No. 5,580,945 11. U.S. Patent No. 5,478,596 12. PCT International Patent Publication WO 2000/01665

The present invention has been made in consideration of the above problems, and in the present invention, a coating composition is prepared by mixing agent A containing isocyanate, agent B containing a curing agent, and a Na ₂ CrO ₄ /C complex, and using the same. Therefore, we would like to present a construction method for protruding lanes with excellent crack resistance and luminance retention in rainy weather at night.

One aspect of the present invention for achieving the above object is (A) obtaining a coating composition by mixing agent A containing isocyanate and agent B containing a curing agent, (B) preparing the coating composition for 40- Heating to 80 ° C., (C) discharging the coating composition onto the road surface at a discharge pressure of 1,500-2,000 psi while maintaining the temperature at 40-80 ° C. and drying the protruding lane construction method. As, the coating composition contains 0.5-1.0 parts by weight of the Na ₂ CrO ₄ /C composite based on 100 parts by weight of the coating composition, and relates to a road marking construction method.

According to the present invention, a coating composition is prepared by mixing agent A containing isocyanate, agent B containing a curing agent, and functional additives, and using the mixture, protruding lanes with excellent crack resistance and luminance retention in rainy weather at night are constructed. can do.

In addition, the paint or composition for coating lanes according to the present invention is based on polyurea, so the drying time is very fast, less than 1/10 of that of general methyl methacrylate (MMA)-based protruding lanes, and It has a particularly advantageous strength for construction in winter, and has an eco-friendly advantage as it is made of 100% solids without volatile substances.

In addition, the protruding lane according to the present invention has strong durability and weather resistance, so it has excellent visibility of the road, especially at night and in rainy weather, compared to existing roads, has excellent anti-slip function and drainage, and unlike existing roads, it can cause drowsy driving. It can be very effective for safe driving as it can recognize the warning sound generated when lane departure occurs.

1a and 1b are photographs showing examples of actual construction of protruding lanes as in the present invention.
Figure 2 shows that the protruding lanes according to the present invention can be constructed in various intervals and patterns (eg, 3x3 or 3x4 method) according to the construction site (tunnel road or main road).

In the following, various aspects and various embodiments of the present invention are described in more detail.

One aspect of the present invention is (A) obtaining a coating composition by mixing agent A containing isocyanate and agent B containing a curing agent, (B) heating the coating composition to 40-80 ° C., (C ) It relates to a protruding lane construction method comprising the steps of discharging and drying the coating composition in a protruding shape on the road surface at a discharge pressure of 1,500-2,000 psi while maintaining the temperature of the coating composition at 40-80 ° C.

At this time, it is important that the coating composition includes 0.5-1.0 parts by weight of the Na ₂ CrO ₄ /C complex based on 100 parts by weight of the coating composition. As described above, in the present invention, the Na ₂ CrO ₄ /C composite, which is a functional additive for protruding lanes, is used. The Na ₂ CrO ₄ /C composite is used in an amount of 0.5-1.0 weight based on 100 parts by weight of the coating composition composed of the agent A and the agent B. part is used

When the above functional additives are used in the above content, crack resistance and luminance retention, especially in the case of rain at night, greatly increase, whereas when the above functional additives are not used or when the above content is out of the above range, the crack resistance is remarkably In addition, it was confirmed that there was almost no decrease in luminance due to abrasion, so that luminance maintenance of almost the same level of luminance value could be secured until the life of the lane expired.

According to one embodiment, the curing agent may be one or more amines selected from Formula 1 below.

[Formula 1]

In the above formula,

(i) X is an alkyl, alkylene, aryl or arylene of valency n;

(ii) R ₁ , R ₂ , R ₄ and R ₅ are the same as or different from each other, and are each independently selected from hydrogen, a C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ aryl group;

(iii) R ₃ is alkyl or aryl;

(iv) n is an integer greater than or equal to 1;

According to the present invention, the lines among the lanes are constructed by the direct injection method commonly used in the industry, and the protrusions can also be constructed by the room temperature drop method of the computer automatic control method commonly used in the industry. For example, Korean Patent No. 10-097798 It can be constructed using arc lane painting equipment and the like.

In addition, as exemplarily shown in FIG. 2 , the protruding lanes according to the present invention may be constructed in various intervals and patterns (eg, 3x3 or 3x4) according to the construction site (tunnel road or main road).

Hereinafter, other aspects and embodiments of the present invention will be described in detail.

In the present invention, a secondary amine represented by Chemical Formula 1 may be used as a curing agent.

[Formula 1]

In the above formula, X is an alkyl, alkylene, aryl or arylene having a valence of n, R ₁ , R ₂ , R ₄ and R ₅ are each independently H, alkyl or aryl, and R ₃ is an alkyl or aryl; , n is an integer greater than or equal to 1.

In addition, in the present invention, an amide-ester precursor of Chemical Formula 2 described below may be prepared using an organotin salt as a catalyst.

In addition, in the present invention, a polyurea coating composition derived from an isocyanate-reactive component including a polyisocyanate component and at least one compound corresponding to a secondary amine is applied.

In addition, in the method for producing the polyurea coating composition of the present invention, a substrate is coated with an isocyanate-reactive component including a polyisocyanate component and at least one compound corresponding to a secondary amine, and then the composition is cured at a temperature of 10-80 ° C. made by doing

The present invention also includes a binder containing a polyurea functional group, which binder comprises an amine component comprising at least one secondary amine as defined above and optionally at least one amine-functional co-reactant, and at least one polyisocyanate. A two-component liquid road sign prepared from a two-component coating composition containing an isocyanate component is provided. Preferably, the road marking comprises a binder containing a urea functional group, which binder comprises an amine component comprising at least one secondary amine as defined above and optionally at least one amine functional co-reactant, and at least one poly It is prepared from a two-part coating composition comprising an isocyanate containing isocyanate, which coating composition has a lowest application temperature of about 10 DEG C or higher and a track free time of about 5 minutes or less. The present invention also provides a road sign and a traffic-related surface having a pre-formed road sign thereon, wherein the composition is coated on a substrate applicable to the traffic-related surface.

In addition, the present invention also provides a method of applying the composition. For example, a method for marking traffic-related surfaces is provided. The method involves applying a two-part coating composition comprising an amine component comprising at least one secondary amine and optionally at least one amine-functional co-reactant to a traffic-related surface, and an isocyanate component comprising at least one polyisocyanate. It includes the application step.

In the above formula (1), the alkyl group is a paraffinic hydrocarbon group derived from an alkane by removing one hydrogen from the above formula. The hydrocarbon group may be straight chain, branched chain, or cyclic when R ₁ and R ₂ are bonded together with nitrogen, and has 1 to 20 carbon atoms. The hydrocarbon preferably has 1 to 5 carbon atoms. Simple examples are methyl and ethyl.

An aryl group is an unsaturated hydrocarbon group having an aromatic ring structure such as benzene or naphthalene, that is, a 6-membered carbon ring of benzene or a condensed 6-membered carbon ring of other aromatic derivatives. Aromatic rings may be substituted or unsubstituted. Possible substituents include alkyl, amino, nitro, hydroxyl, halogen and methoxy functional groups. A simple example of an (unsubstituted) aryl group is phenyl.

An isocyanate group is a compound containing an isocyanate radical (-NCO). The term isocyanate refers to polyisocyanates, preferably diisocyanates or triisocyanates.

An arylene group is a multivalent radical formed by removing hydrogen from two or more carbon sites of an aromatic nucleus.

An alkylene group is an organic radical formed by removing hydrogen from two or more carbon sites of an aliphatic hydrocarbon. A simple example is the ethylene radical, -C ₂ H ₄ -.

As previously discussed, secondary amines can be produced via Michael type reactions of primary amines with various amide-esters. Michael acceptors useful as precursors include addition reaction products of alcohols and isomaleimides. This reaction is shown below as giving the compound.

[Scheme 4]

The desired product can be obtained in increased yield by using an organotin salt as a catalyst. The method of the present invention reacts the isomaleimide with an alcohol, R ₃ OH in the presence of an organotin catalyst to obtain a product of the reaction formula (wherein R ₂ is an alkyl or aryl group, and R ₃ , R ₄ and R ₅ are as defined above).

The reaction between isomaleimide and alcohol may be carried out at about 0 to about 100 °C, preferably room temperature, that is, about 25 to about 70 °C. Examples of organotin salts usable as catalysts include dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dilaurate, stannous octoate, bis(lauryldibutyltin) oxide, and dibutyltin dimercaptide. and dibutyltin dimercaptide. A preferred catalyst is dibutyltin diacetate. The amount of catalyst used may vary from about 0.1 to about 10 mole percent based on the amount of alcohol. The isomaleimide starting material can be prepared by a known method.

An alternative method of making amide ester precursors involves reacting maleic anhydride with an amine, followed by conversion of the carboxylic acid group to the desired ester. This reaction is

[Scheme 5]

In the above formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined above, and Hal represents a halide ion, preferably iodide.

The reaction of primary amines with amide-ester Michael acceptors is often spontaneous, rapid, and occurs almost quantitatively. This addition reaction product can be synthesized simply by allowing a mixture of a primary amine and a Michael acceptor to stand at about 70° C. for about 96 hours in the presence of a catalyst. This reaction is

[Scheme 6]

In the above formula, X, n and R ₁ -R ₅ are as defined above.

Examples of amines useful in preparing the secondary amines of the present invention include ethylenediamine, 1,2-diaminopropane, 2,5-diamino-2,5-dimethylhexane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,4'-diamino-dicyclohexylmethane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- or 2,6 -Diaminotoluene, 2,4'- or 4,4'-diaminodiphenyl methane or mixtures thereof. Preferred amines for preparing secondary amines are 1,4-diaminobutane, 1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 1-amino-3,3 ,5-trimethyl-5-aminomethyl-cyclohexane, 4,4'-diamino-dicyclohexylmethane, 3,3-dimethyl-4,4'-diamino-dicyclohexylmethane or mixtures thereof . Particularly preferred amines are 4,4'-methylene-bis(cyclohexylamine), 2-methyl-1,5-pentanediamine, 1,6-diaminohexane and mixtures thereof.

The reaction is generally 80%-99% complete within 96 hours. Since the reaction is clean, purification of the reaction product is unnecessary.

These hindered secondary amines react with nucleophiles with greater control than the corresponding primary amines, and hydrogen bonds in these addition reaction products are significantly reduced or eliminated. Secondary amines react with isocyanates to form urea-amide/ester bonds. This reaction accounts for the formation of the following compounds.

[Scheme 7]

In the above formula, X, R ₁ , R ₂ and R ₃ are as defined above, and Y is X.

Unlike urea-diester bonds, urea-amide/ester bonds are stable. Amide-esters do not cyclize to hydantoin. Hydantoin causes contraction and is formed with a urea-diester linkage as described above.

Further, the present invention relates to a polyurea coating composition having an isocyanate-reactive component containing a polyisocyanate and at least one compound corresponding to a secondary amine as described above. The crosslinking that takes place in the process of the present invention is based on an addition reaction between the polyisocyanate component and the isocyanate-reactive component, in particular a secondary amine.

Polyisocyanate refers to a compound having one or more isocyanate groups, and includes known polyisocyanates in polyurethane chemistry. Suitable low molecular weight polyisocyanates with a molecular weight of 168-5,000 include hexamethylene diisocyanate, 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate , 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'- and/or 4 ,4'-diisocyanatodicyclohexyl methane, 2,4'- and 4,4'-diisocyanato-diphenylmethane and their isomers, and aniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotoluene and mixtures with higher homologs prepared by phosgenation of any mixtures of these compounds.

However, it is preferred to use derivatives of these monomeric polyisocyanates. These derivatives include, for example, polyisocyanates containing biuret (carbamylurea) groups as described in U.S. Pat. Nos. 3,124,605, 3,201,372, and DE-OS 1,101,394; polyisocyanates containing isocyanate groups as described, for example, in U.S. Patent Nos. 3,001,973, DE-PS 1,022,789, 1,333,067 and 1,027,394, and DE-OS 1,929,034 and 2,004,048; polyisocyanates containing urethane groups as described, for example, in DE-OS 953,012, BE-PS 752,261, and US Pat. Nos. 3,394,164 and 3,644,457; polyisocyanates containing carbodiimide groups as described, for example, in DE-OP 1,092,007, U.S. Patent No. 3,152,162 and DE-OS 2,504,400, 2,537,685 and 2,552,350; and polyisocyanates containing allophanate groups as described, for example, in GB-PS 994,890, BE-PS 761,626 and NL-OS 7,102,524.

Modified polyisocyanates are particularly preferred. For example, N,N',N"-tris-(6-isocyanatohexyl)-biuret and mixtures of its higher homologues, and N,N',N"-tris-(6-isocyanatohexyl) )-isocyanurates and mixtures of them with higher homologues containing at least one isocyanurate ring.

Prepolymers and semi-prepolymers containing an isocyanate group containing a simple polyisocyanate or a modified polyisocyanate of monomeric nature as a main component and an organic polyhydroxyl compound as exemplified above are preferable for use as the polyisocyanate component. These prepolymers and semi-prepolymers generally have about 140-8,400 equivalents, preferably about 210-420 equivalents, and use the aforementioned starting materials in an NCO/OH equivalent ratio of about 1.05:1-10:1, preferably about 1.1: It is prepared using a known method in which, after a 1-3:1 reaction, optionally distilling off any unreacted volatile starting polyisocyanates present.

Prepolymers and semi-prepolymers are low molecular weight polyhydroxyl compounds of molecular weight 62-299, such as ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxyhexane; low molecular weight hydroxyl-containing esters of the types described below of these polyols with dicarboxylic acids; low molecular weight ethoxylation and/or propoxylation products of these polyols; and mixtures of these polydenatured or undenatured alcohols.

However, prepolymers and semi-prepolymers are prepared from known relatively high molecular weight polyhydroxyl compounds of polyurethane chemistry having molecular weights, as measured by functionality and OH number, ranging from 300 to about 8,000, preferably from about 1,000 to 5,000. These polyhydroxyl compounds have two or more hydroxyl groups per molecule and generally have a hydroxyl group content of about 0.5-17% by weight.

Examples of suitable relatively high molecular weight polyhydroxyl compounds that may be used in the preparation of prepolymers and semi-prepolymers include the aforementioned low molecular weight monomeric alcohols and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, phthalic acid, tetra-hydrophthalic acid, hexahydrophthalic acid, maleic acid), polyester polyols based on anhydrides of these acids and mixtures of these acids and/or acid anhydrides. Polylactones containing hydroxyl groups, in particular poly-e-caprolactone, are also suitable for the production of prepolymers and semi-prepolymers.

Polyether polyols prepared in a known manner by alkoxylation of molecules of suitable starting materials are also suitable for the production of prepolymers and semi-prepolymers containing isocyanate groups. Examples of suitable starter molecules for polyether polyols are the aforementioned monomeric polyols, water, organic polyamines having two or more NH bonds, and any mixtures of these starter molecules. Ethylene oxide and/or propylene oxide are alkylene oxides particularly suitable for alkoxylation reactions. These alkylene oxides may be introduced into the alkoxylation reaction in any order or as a mixture.

Polycarbonates containing hydroxyl groups, which can be prepared by reaction of the aforementioned monomeric diols with phosgene and diaryl carbonates such as diphenyl carbonate, are also suitable for the preparation of pre- and semi-prepolymers.

These other optionally used isocyanate-reactive compounds are preferably organic polyhydroxyl compounds known from polyurethane chemistry and are relatively low molecular weight polyhydroxyl compounds described above for the preparation of prepolymers and semi-prepolymers suitable for use as polyisocyanate components. Both high molecular weight polyhydroxyl compounds are mentioned.

Isocyanate-reactive compounds that can be used as part of the polyisocyanate component are hydroxy functional polyacrylates known for use in polyurethane coatings. These compounds have a number average molecular weight (M _n ) of about 800-50,000, preferably about 1000-20,000, more preferably about 5,000-10,000, as measured by vapor pressure or membrane osmometry, and a hydroxyl group content of about 0.11-10,000. 12% by weight, preferably about 1-10% by weight, most preferably about 2-6% by weight of a hydroxyl-containing copolymer of olefinically unsaturated compounds. This copolymer mainly contains an olefinic monomer containing a hydroxyl group and an olefinic monomer having no hydroxyl group. Examples of suitable monomers include vinyl and vinylidene monomers (eg styrene, α-methylstyrene, o- and p-chlorostyrene, o-, m- and p-methyl styrene, p-tert-butyl styrene), acrylic acid, ( methyl)acrylonitrile, acrylic acid and methacrylic acid esters of alcohols containing 1 to 8 carbon atoms (e.g., ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and iso-octyl methacrylate), fumaric acid with 4-8 carbon atoms in the alcohol component , diesters of itaconic acid or maleic acid, (methyl)acrylic acid amides, vinyl esters of alkane monocarboxylic acids having 2 to 5 carbon atoms (such as vinyl acetate or vinyl propionate), and carbon atoms in hydroxyalkyl groups 2-4 hydroxyalkyl esters of acrylic or methacrylic acid, such as 2-hydroxyethyl-, 2-hydroxypropyl-, 4-hydroxybutyl-acrylates and methacrylates and trimethylol propane- mono- or pentaerythritomono-acrylate or methacrylate). In addition, mixtures of the monomers exemplified above can also be used for the preparation of hydroxy functional polyacrylates. Mixtures of the aforementioned polyhydroxy compounds may be used as part of the polyisocyanate component.

In coating compositions intended for use in the method of the present invention, the weight ratio of the total amount of binder components to the amount of solvent is about 40:60-100:0, preferably about 60:40-100:0.

In addition, the coating composition to be used in the method of the present invention may include other auxiliary agents and additives conventionally used in polyurethane coatings, particularly pigments, fillers, leveling agents, catalysts, anti-settling agents, antioxidants, UV stabilizers, and the like.

The properties of the coating produced according to the method of the present invention can be controlled, in particular by properly selecting the nature and proportions of the starting components. Thus, for example, the presence of a relatively high molecular weight straight-chain polyhydroxyl compound in the prepolymer or semi-prepolymer of each component increases the elasticity of the coating, whereas the absence of such a starting component increases the crosslinking density and hardness of the resulting coating. do.

To carry out the method of the present invention, the coating composition to be used in the method of the present invention is applied in one or two layers by known methods, such as spraying, brush coating, impregnation or flooding, or roller Alternatively, it is applied to the substrate using a doctor applicator. The method of the present invention is suitable for forming a coating on any substrate (eg metal, plastic, wood or glass). After the substrate to be coated by the method of the present invention is first treated with an appropriate primer, the method of the present invention can be performed.

After coating the previously exemplified substrate, the coating is cured at a temperature of about -20 to 100 °C according to the method of the present invention. Curing is preferably carried out at a temperature of about 10-80 °C.

The present invention provides a two-component liquid road sign containing a binder having a polyurea group, wherein the binder comprises an amine component comprising at least one secondary amine as defined above and optionally at least one amine-functional co-reactant; It is prepared from a two-component coating composition comprising an isocyanate component containing the above polyisocyanate. Preferably, the road sign contains a binder having urea functionality, which binder contains an amine component having at least one secondary amine and optionally at least one amine functional co-reactant, and at least one polyisocyanate. It is prepared from a two-component coating composition comprising an isocyanate component, which coating composition has a minimum application temperature of about 10 DEG C or higher and a track free time of about 5 minutes or less.

The equivalent ratio of isocyanate functional groups to isocyanate reactive groups in the binder used according to the present invention is about 0.8 : 1-20 : 1, preferably about 0.8 : 1-2 : 1, more preferably about 0.8 : 1-1.2 : 1 , most preferably about 1:1. Any polyhydroxyl compound is such that no more than 20 hydroxyl groups are present for each secondary amino, preferably the equivalent ratio of hydroxyl groups to secondary amino groups is from about 10:1 to about 1:10. present in the amine component in an amount that allows

The binder to be used in the present invention is prepared by mixing the respective components together. The preparation of the binder is carried out in the absence of solvents or in the presence of solvents conventionally used for polyurethane coatings. It is an advantage of the process of the present invention that the amount of solvent used can be greatly reduced when compared to that required in known two-component systems.

Examples of suitable solvents are xylene, butyl acetate, methyl isobutyl ketone, methoxypropyl acetate, N-methyl pyrrolidone, petroleum hydrocarbons, isobutanol, butyl glycol, butoxyethanol, chlorobenzene and mixtures of these solvents. . The alcohol-based solvents described above may be used, but in this case, any polyhydroxyl compound is not used.

The road marking composition of the present invention contains a binder containing a urea group. This binder is prepared from a two component system comprising an amine compound and an isocyanate component. Preferably, the amine component includes a secondary amine. More preferably, the amine component includes a secondary amine of the present invention. Most preferably the amine component comprises one or more amide-ester amines, optionally blended with one or more amine functional co-reactants instead of one amide-ester amine. The amine functional co-reactant is preferably a polymeric polyamine, more preferably a substantially polymeric diamine. These amine functional co-reactants are selected to match the properties of the coating during the curing process with the properties of the coating in its final form.

The amine and isocyanate components are selected so that the manufactured road signs are generally resistant, durable to environmental and vehicular stress, and have good daytime visibility. It is also desirable to have good night visibility. Durability is manifested in excellent adhesion (i.e., fixation) to various substrate surfaces, including concrete, asphalt, and other substrates, whether the road sign and the substrate are the same material or different materials. In addition, durability is also manifested in excellent adhesion (i.e. fixation) of any reflective part to the mark. In this specification, "durability" may be measured by applying a road sign to a road surface that will be exposed to a traffic environment and monitoring the performance of the sign over time. Reflectivity and whiteness can be measured using instruments of the art, and resistance to abrasion and corrosion of a marker can be evaluated subjectively. Durable markers are continuously present on the substrate and have good visibility and, preferably, good reflectivity over an extended period of time.

Road signs formed from the compositions of the present invention are durable (i.e., have a useful lifetime) for at least about 2 years, more preferably at least about 3 years, and most preferably at least about 4 years. When reflective components are used, the road sign retains a reflectivity of greater than about 100 mcd/m ² /lux, more preferably greater than about 150 mcd/m ² /lux during its useful life. In this specification, the term "retained reflectance" is used to indicate the effectiveness of a road sign's retroreflective performance maintained over its useful life. Retroreflectivity is now typically measured by laboratory instruments at fixed angles of incidence and observation according to ASTM D 4061-94. A recent study (Transport Research Record 1409, published in 1994 by the Transport Research Institute), also referred to as "approximate driver geometry", shows that the angle of incidence of a ray of light and the angle of observation at which a driver actually sees a road sign is a reflection of the road sign's retroreflection. suitable as a measure of performance.

The amine and isocyanate components are preferably selected such that the road marking composition has the following characteristics:

(1) substantially free of solvents (preferably less than about 5% solvent by weight based on the total weight of the composition), high solids content (preferably greater than about 75% by weight based on the total weight of the composition, more preferably is a liquid having at least about 90% by weight),

(2) has a fast cure profile, and a track free time (i.e., drying under ambient road conditions when the coating is applied) is preferably about 5 minutes or less, more preferably about 4 minutes or less, and most preferably about 4 minutes or less; 3 minutes or less, and a useful open time (i.e., the time during which the composition remains free flowing after being applied to a substrate for adequate substrate wetting and particle or reflective component wicking/fixation) is preferably about 30 seconds. or more, more preferably about 1 minute or more,

(3) It has a wide application window (ie, it can be applied over a wide range of temperatures (especially low temperatures)).

(4) It can be used with a two-component static mixing application device or an airless high-pressure impingement mixing application device;

(5) made of commercially available low-cost raw materials;

(6) They are generally shelf stable, preferably having a useful shelf life of at least 6 months, more preferably at least 1 year, and most preferably at least 2 years.

Although the road marking composition of the present invention is referred to as a two-part composition, many additives may also be included. These additives include weathering additives, antioxidants, dispersing aids, grinding aids, wetting agents, impact modifiers, defoamers, pigments, fillers, extenders, diluents, plasticizers, leveling agents and surfactants.

Pigments are known in the road sign art to impart a certain visual appearance during the day and to contribute to the reflectivity of signs at night. Fillers and extenders can be used to modify the flow properties of liquid coatings and can contribute to the bulk volume of the final coating. Fillers can also be used to achieve specific volume ratios without significantly affecting the reaction chemistry. Pigments, fillers and extenders have a significant effect on uncured formulation and cured film density, film cure profile and track free time, cured film modulus, coating adhesion to substrate, response to thermal cycling, wear and coating durability. can

comprising applying to a traffic related surface a two part coating composition comprising an amine component comprising at least one secondary amine and optionally at least one amine functional co-reactant and an isocyanate component comprising at least one polyisocyanate. A method for marking traffic-related surfaces that

The two-part coating composition is typically applied using a spray coating technique. Typically, the two components are applied using a spray device, from which they are mixed just prior to discharge. For example, a two-component, high pressure, airless, impingement mixing system may be used. An example of an airless, impingement mix spray system is manufactured by Gusmer. The system includes a proportional zone that meters the ingredients and increases the pressure to about 1500 psi or more, a heating zone that controls the viscosity of each ingredient, and an impingement spray gun that combines the two ingredients and mixes them just before spraying.

Another useful system is similar to the impingement unit above except that it uses a static mixing tube to achieve the two component blending. This mixing tube has a number of vanes designed to mix the ingredients prior to spraying.

It is noteworthy that this liquid road marking composition provides a polyurea coating with conventional daytime visibility. In addition, this composition can also act as a binder for fixing the reflective optical component. If the reflective component is a glass or ceramic microsphere, it is typically in the range of about 100 to 600 μm and can be incorporated into the coating or preferably dripped onto a wet coating.

Parts in the form of glass or ceramic microspheres applied after spraying can also be used as binder fillers in addition to providing night reflectivity. They act similarly to mineral particles on the wear surface. A typical coverage rate is preferably about 4 pounds or more of glass beads per gallon of paint, more preferably about 10 pounds or more, even more preferably about 25 pounds or more, and most preferably about 30 pounds or more.

Hereinafter, the present invention will be described in more detail through examples and the like, but the scope and contents of the present invention are reduced or limited by the examples below and cannot be interpreted. In addition, based on the disclosure of the present invention including the following examples, it is clear that a person skilled in the art can easily practice the present invention for which no experimental results are specifically presented, and the patents to which such variations and modifications are attached. It goes without saying that it falls within the scope of the claims.

In addition, the experimental results presented below are only representative experimental results of the above examples and comparative examples, and each effect of various embodiments of the present invention that is not explicitly presented below will be described in detail in the corresponding section.

Example

manufacturing example

The Na ₂ CrO ₄ /C composite was prepared by ball milling as follows. First, Na ₂ CrO ₄ (98.0%) and carbon black were purchased from Sigma-Aldrich and used without additional modification. A ceramic bowl containing a mixture of Na ₂ CrO ₄ and carbon black in a stoichiometric ratio was assembled in an argon atmosphere in a glove box to prevent moisture impregnation. The mixture was milled using a zirconium ball, and milling was performed at 300 rpm for 24 hours.

Example 1

As described in Example 3 of WO 2000/01665, four different diisocyanates and secondary amines are mixed in stoichiometric proportions based on the equivalent weight of each material, so that their total weight is 100 g did A projecting lane composition was prepared by adding 0.75 g of the Na ₂ CrO ₄ /C composite prepared in Preparation Example above.

Comparative Example 1

A protruding lane composition was prepared in the same manner as in Example 1, except that the Na ₂ CrO ₄ /C composite prepared in Preparation Example was not used.

Comparative Example 2

A projecting lane composition was prepared in the same manner as in Example 1 above, except that 0.3 g of the Na ₂ CrO ₄ /C composite prepared in Preparation Example was added instead of 0.75 g.

Comparative Example 3

A projecting lane composition was prepared in the same manner as in Example 1 above, except that 1.2 g of the Na ₂ CrO ₄ /C composite prepared in Preparation Example was added instead of 0.75 g.

Test Example 1: Crack resistance test

The protruding lane composition prepared in Examples and Comparative Examples 1 to 3 was discharged onto the test floor and cured to construct a test specimen lane, and then the crack resistance of the protruding lane material was observed. To this end, an actual crack resistance test was performed under the following conditions according to EN 1463L2007 standard.

- Test tire: use a passenger car tire or equivalent

- Number of tires: 2

- Load on tire wheel: 3,000 N

- Tire air arm: 0.25 MPa

- Support angle: 0ㅀ or more

- Steering angle: alternating ㅁ 1ㅀ or more

- Rotation speed: average 60 km/h

- Running cycle: Rotate the dried test plate until it reaches 200,000 revolutions. The direction of rotation is changed approximately every 16 h of test time.

- Test temperature: 5-10℃

As a result, no cracks were observed in the suboptimal specimens prepared in Examples, whereas cracks were visually observed in all specimens, although there were differences in size and number in suboptimal specimens prepared in Comparative Examples 1 to 3.

Test Example 2: Observation of decrease in luminance

The luminance was first measured for the lane specimens constructed in Test Example 1 above, and then the luminance was measured secondarily for each specimen after the driving cycle in Test Example 1 above. The luminance measured first and secondly was measured by the wet recovery test method for the luminance of night rainy weather lane painting according to the lane painting standard Ministry of Transportation-1337.

As a result, the sub-optimal specimens prepared in Examples did not show a large change between the first and second luminance measured values, whereas the specimens manufactured in Comparative Examples 1 to 3 showed a second luminance value compared to the first luminance measured value. It was confirmed that the measured luminance values decreased by 56%, 34%, and 23%, respectively.

Claims (2)

(A) obtaining a coating composition by mixing agent A containing isocyanate and agent B containing a curing agent;
(B) heating the coating composition to 40-80 °C;
(C) a protruding lane construction method comprising the step of discharging the coating composition onto a road surface in a protruding shape at a discharge pressure of 1,500-2,000 psi while maintaining a temperature of 40-80 ° C and drying it,
The coating composition includes 0.5-1.0 parts by weight of the Na ₂ CrO ₄ /C complex based on 100 parts by weight of the coating composition,
The curing agent is one or more amines selected from Formula 1 below,
[Formula 1]

In the above formula,
(i) X is an alkyl, alkylene, aryl or arylene of valency n;
(ii) R ₁ , R ₂ , R ₄ and R ₅ are the same as or different from each other, and are each independently selected from hydrogen, a C ₁ -C ₂₀ alkyl group, and a C ₁ -C ₂₀ aryl group;
(iii) R ₃ is alkyl or aryl;
(iv) a protruding lane construction method, characterized in that n is an integer greater than or equal to 1. The method of claim 1, wherein the protruding lane construction method comprises: (D) simultaneously spraying reflective parts selected from glass microspheres, ceramic microspheres, and mixtures thereof on the road surface onto which the coating composition is sprayed, simultaneously with the step (C). Protruding lane construction method, characterized in that it further comprises a step.

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