KR101325529B1 - Paint for road painting and manufacturing method thereof - Google Patents

Abstract

Described is a thermosetting two-component polyurethane paint for indicating road lane comprising a prepolymer base part, a hardener part, and two-component and room temperature vulcanizing thermosetting polyurethane resin, in which the mixing ratio of the prepolymer base part to the hardener part is 0.5-2 to 1 in weight ratio, as solid contents. Here, the prepolymer base part is obtained by polymerizing 5-31 wt% of high equivalent polyol, 5-60 wt% of low equivalent polyol and residual amount of polyisocyanate, wherein the content of unreacted free isocyanate is 9-20 wt%; and the hardener part comprises 0.01-3 wt% of catalyst, 30-65 wt% of low equivalent polyol, 0.5-3 wt% of polyoxyethylenglycol with 200-400 of number average molecular weight as an accelerating admixture, 1-30 wt% of additive, and residual amount of pigment.

Description

Paint for thermosetting two-component polyurethane road lane marking and its manufacturing method {Paint for road painting and manufacturing method}

The present invention is a thermosetting two-component polyurethane road lane The present invention relates to a display paint and a method for manufacturing the same, and more particularly, to an eco-friendly, two-component polyurethane resin-based thermosetting two-component polyurethane road lane containing no volatile harmful substances, polyaromatic hydrocarbons, and noxious heavy metals. A display paint and a manufacturing method thereof.

Conventional road paints, especially those used for lane markings, are boiled and melted by vapor pressure up to about 200 ° C using the properties of asphalt, and then transferred to a conventional painter to paint a thickness of about 2 mm on the road surface. As the hot heat of the paint material melts the surface layer of the asphalt constituting the roadway, the surface layer becomes tacky due to the petroleum components present in the surface layer, and the coating layer is formed on the surface of the asphalt by the adhesion.

However, the coating using the conventional road lane marking paint as described above, the adhesive strength of the tar component varies according to the aging degree of the asphalt material, the difference in adhesive strength also occurs depending on the ratio of the tar component and aggregate, etc. Since there are many variables that make it difficult to achieve a certain level of adhesion, there is a problem that quality control of the paint part becomes difficult.

In addition, the conventional road lane marking paint is not adhesive because it is impossible to install at less than -5 ℃, even if the construction will be broken (broken) in a few days. In addition, in winter, the mechanical properties such as tensile elongation of the paint material is low, so there is a problem that the damage is inevitable and easy to repair. The adhesion problem of the conventional road lane marking paint is inevitably dependent on the special components of the primer applied to the roadway when applied to cement roads.

In particular, the urethane resin used in the manufacture of conventional road lane marking paints is a two-part type, comprising a prepolymer main portion and a curing agent portion, wherein the prepolymer main portion is synthesized from an isocyanate such as toluene diisocyanate (TDI) and a long chain polyol. Containing unreacted isocyanate groups at the terminal The main component is a urethane prepolymer, and the curing agent portion is an aromatic diamine (for example, 4,4'-methylenebis (2-chloroaniline); hereinafter abbreviated as 'MOCA') and a long-chain polyol which react with the isocyanate of the urethane prepolymer. It is made to include, and the curing agent portion is further added to the catalyst such as organometallic, lead, or plasticizer if necessary. Alternatively, the prepolymer main portion is composed mainly of a prepolymer having an isocyanate group at the terminal synthesized by the reaction of an aromatic diisocyanate or aliphatic diisocyanate with a polyether polyol and / or a low molecular glycol, a monoepoxide modified diamine curing agent and a diamine curing agent, It is a structure in which the unreacted free isocyanate generally reacts and cures with MOCA, a lead catalyst or a monoepoxide-modified diamine curing agent and a diamine curing agent in a range of 4 to 8% using a curing agent portion including an additive such as a plasticizer. These conventional two-component polyurethanes include volatile harmful substances, polyaromatic hydrocarbons, and harmful heavy metals, and when applied to roads such as lanes using conventional road lane marking paints made of such polyurethane, Although it is stable in performance, it is separated and / or decomposed over time due to friction with a car tire driving thereon, thereby releasing the above volatile harmful substances, polycyclic aromatic hydrocarbons and harmful heavy metals into the atmosphere. In addition, there is a problem in that it must be an unfriendly environment that can adversely affect the health of pedestrians, as well as motorists.

One object of the present invention is to display lane marking paints on roads, especially cement roads. Two-part thermosetting as a road lane marking paint that can have excellent properties such as sufficient adhesive strength and elongation on the road surface without the use of a separate primer in the coating operation To provide a polyurethane.

Another object of the present invention is a two-part thermosetting as a road lane marking paint that can be solidified by reacting in a few seconds to several minutes. To provide a polyurethane.

Another object of the present invention is to contain a relatively large amount of unreacted free isocyanate without using a polycyclic or monocyclic aromatic crosslinking agent, so that the ethoxy adduct and the number of low molecular weight polyols based on the number average contained in the curing agent portion It is to provide a two-component thermosetting polyurethane as a road lane marking paint capable of rapid curing by exothermic reaction between an average reference low molecular weight polyoxyethylene glycol and unreacted free isocyanate.

Another object of the present invention is a two-component thermosetting as a road lane marking paint of a non-foaming mechanism in which foaming does not occur at all in order to maintain proper physical properties as a road lane marking paint. To provide a polyurethane.

Still another object of the present invention is a two-component thermosetting as an environmentally friendly road lane marking paint that does not contain volatile harmful substances, polyaromatic hydrocarbons and harmful heavy metals. To provide a polyurethane.

Still another object of the present invention is to provide a thermosetting two-component polyurethane road lane marking paint that can be applied by a simple equipment without a device for applying heat unlike conventional road marking paints.

The road lane marking paint according to the present invention comprises a prepolymer main portion and a hardener portion; Wherein the prepolymer main portion is 5 to 31% by weight of high equivalent polyol, 5 to 60% by weight of low equivalent polyol And a content of 9 to 20% by weight of the unreacted free isocyanate obtained by polymerizing the polyisocyanate as the remainder; The hardener is 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance Including; The mixing ratio of the prepolymer main portion: the curing agent portion is mixed in a weight ratio of 0.5 to 2: 1.

The prepolymer of the prepolymer main portion preferably has a number average molecular weight within the range of 5,000 to 30,000.

Preferably, the low equivalent polyol has an equivalent within the range of 100 to 277, and the high equivalent polyol preferably has an equivalent within the range of 330 to 6,000.

It is preferable that the said catalyst which comprises the said hardening | curing agent part is an amine catalyst, a tin catalyst, or a mixture thereof.

The additive is preferably selected from the group consisting of antisettling agents, antifoaming agents, foam inhibitors, ultraviolet stabilizers, color stabilizers, and mixtures of two or more thereof.

The manufacturing method of the thermosetting two-component polyurethane road lane marking paint which concerns on this invention is a manufacture of the road lane marking paint which consists of a prepolymer main part and a hardening | curing agent part, (1) 5-31 weight% of high equivalent polyol A main part manufacturing step of polymerizing the polyisocyanate as a low equivalent polyol of 5 to 60% by weight and the remaining amount to prepare a prepolymer having an unreacted free isocyanate content of 9 to 20% by weight; (2) 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance A curing agent part manufacturing step of mixing the pigment to prepare a curing agent part; And (3) a packaging step of packaging the prepolymer main portion: a curing agent portion at a ratio of 0.5 to 2: 1 by weight ratio.

According to the present invention, a two-component thermosetting property as a paint for road lane marking capable of rapid curing that can be used in road lane marking and the like. Polyurethane is a thermosetting two-component polyurethane that can not only provide better adhesion and durability than conventional products, but also can work with simple equipment while providing high durability and strong adhesion, which can contribute to high economic effect and energy saving. It is effective to provide paint for road lane markings.

In addition, according to the present invention, it does not include volatile harmful substances as diluents, polyaromatic hydrocarbons as tensile elongation modifiers, and harmful heavy metals as catalysts, which is environmentally friendly and minimizes factors that may adversely affect the health of drivers and pedestrians. Provides thermosetting two-component polyurethane road lane marking paint that eliminates hazards, increases durability, and is applied by simple equipment, i.e., a heat-free mixing device, without the need for primers on low cost and winter cement roads. As it is applied, low emissions of carbon dioxide (CO ₂ ), which are a problem for the greenhouse effect, have the effect of reducing traffic jams with eco-friendly and low-cost winter work and fast curing and simple equipment.

By using the thermosetting two-component polyurethane road lane marking paint according to the present invention, the lanes with excellent durability can be easily applied at one time in four seasons and asphalt roads as well as on cement roads without the use of separate primers. It can also provide several advantages, such as being simple to form.

Hereinafter, the present invention will be described in detail with reference to specific embodiments.

The road lane marking paint according to the present invention comprises a prepolymer main portion and a hardener portion; Wherein the prepolymer main portion is 5 to 31% by weight of high equivalent polyol, 5 to 60% by weight of low equivalent polyol And a content of 9 to 20% by weight of the unreacted free isocyanate obtained by polymerizing the polyisocyanate as the remainder; The hardener is 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance Including; Characterized in that the mixing ratio of the prepolymer main portion: the curing agent portion is mixed in a weight ratio of 0.5 to 2: 1.

The thermosetting two-component polyurethane road lane marking paint according to the present invention as described above comprises a two-component thermosetting polyurethane resin capable of reacting a prepolymer main portion with a curing agent to obtain a polyurethane resin constituting a solid of the paint. It is done by

The prepolymer main portion constituting part of the two-part form together with the curing agent portion 5 to 31% by weight of the high equivalent polyol, 5 to 60% by weight of the low equivalent polyol And as a residual amount, are obtained by polymerizing a polyisocyanate. That is, the polyol constituting the prepolymer by reacting with the polyisocyanate is characterized by adjusting the hardness of the polyurethane resin finally obtained by controlling the ratio of the high equivalent polyol and the low equivalent polyol. That is, in the synthesis of the prepolymer, the polyurethane resin finally obtained by controlling the use ratio of the high equivalent polyol and the low equivalent polyol within a range such that the content of unreacted free isocyanate is within the range of 9 to 20% by weight. It is characterized by a point to adjust the hardness of. Here, the term equivalent is used in the same concept as equivalent weight as a general chemical term. It means the total number average molecular weight divided by the number of functional groups, and since the polyisocyanate and polyol react in equivalent ratio, the residual unreacted of the prepolymer obtained by reacting polyisocyanate with polyol, especially high equivalent polyol and low equivalent polyol The content of free isocyanates can be controlled. For example, as the polyisocyanate constituting the prepolymer, monomeric methylene diphenyl diisocyanate (Monomeric MDI, 4,4'-diphenylmethane diisocyanate; Mw = 250.25), polymeric methylene diphenyl diisocyanate ( When polymeric MDI (methylene diphenyl diisocyanate), 4,4'-diphenylmethane diisocyanate (Mw = 286.25) is used, the equivalent of this methylenediphenyl diisocyanate divided by the number of functional groups (= 2), i.e. about 125 (125.13 or 143.13), and the equivalent of toluene diisocyanate (TDI; toluene diisocyanate; Mw = 174.16) is about 88 (87.80). In addition, the polyol can also calculate the equivalent weight as described above, for example, a polyol commercialized as a low equivalent polyol GP-700 (polyol made of a number average molecular weight 700 by adding propylene oxide to glycerin, South Korea, KPX Chemical In the case of Co., Ltd., the equivalent weight is about 233 (233.33). In the present invention, by using a mixture of high equivalent polyol and low equivalent polyol on the basis of the equivalent of the polyisocyanate to control the hardness of the polyurethane resin finally obtained, wherein the low equivalent polyol is within the range of 100 to 277 Having an equivalent weight, Preferably, the high equivalent polyol has an equivalent within the range of 330 to 6,000, but the present invention is not limited thereto, and the number of functional groups relative to the number average molecular weight is high based on the commercialized polyols of the high equivalent polyol and the low equivalent polyol. It can be used separately from the ones. When the equivalent weight of the low equivalent polyol is less than 100, there may be a problem that it is not easy to use because there is no commercialized polyol, and when the equivalent is less than 100, monool is a low equivalent and physical properties are easily broken and reacted upon reaction. Temperature control can be difficult, On the contrary, if it exceeds 277, there may be a problem that the boundary point of the equivalent of the low equivalent polyol is ambiguous, that is, insufficient to synthesize a product having sufficient hardness by using it as the boundary point of hardness control. The reference value of 277, which is the boundary point between the low equivalent polyol and the high equivalent polyol, is a low equivalent and is limited to polyol products having 3 or less functional groups, and the low equivalent 100 is a product having more than 2 functional groups, i.e., 2 to 6 functional groups, among the products currently produced. It can be understood that it is limited to the product of, which is expressed as a number average molecular weight corresponds to 200 to 830. If used in excess of this, the curing rate and hardness may be affected. Based on the current commercially available products, the low equivalent polyol has a number average molecular weight of 700 to 750 and the next commercialized high equivalent polyol product has a number average molecular weight of 1,000. Most of them are.

When the high equivalent polyol used in the preparation of the prepolymer main portion is used in less than 5% by weight based on the total weight of the prepolymer, there may be a problem that no influence on the elongation in mechanical properties may occur, and conversely, 31% by weight. When used in excess of%, there may be a problem that does not exceed the lower limit hardness 70 of the required product.

In addition, when the low equivalent polyol used in the preparation of the prepolymer main portion is used in less than 5% by weight based on the total weight of the prepolymer, there may be a problem that the hardness lower than the hardness of the product does not exceed 70, on the contrary 60 When used in excess of%, there may be problems in controlling the reaction temperature and in obtaining the viscosity of the usable product, and for this reason, commercialization.

The content of the unreacted free isocyanate in the prepolymer obtained above is preferably within the range of 9 to 20% by weight, and when the content of the unreacted free isocyanate is less than 9% based on the total amount of the prepolymer, There may be problems in controlling the curing rate, hardness and viscosity due to the restriction of the use of low equivalent polyols. On the contrary, if it exceeds 20% by weight, the use of the main part is limited due to excessive use of the hardener part due to the inversion of the ratio of the main part and the hardener part. In addition, there may be a problem that it is difficult to perform the function of the lane display paint because the tensile strength elongation is lowered.

It forms part of the two-part form together with the prepolymer main portion, and functions to react with the prepolymer main portion to cure the prepolymer main portion. The catalyst is preferably an amine catalyst or tin catalyst or a mixture thereof. The amine catalyst or the tin catalyst is well known to be used by those skilled in the art and can be purchased and used by domestic and international manufacturers and can be easily understood by those skilled in the art. Examples of the amine catalyst include triethylene diamine (Dabco 33lv, manufactured by Air Products, Inc. of the United States), and examples of the tin catalyst include, for example, stannous octoate; T-9, manufactured by Air Products, Inc., USA, may be used, and these catalysts are widely used in the production of polyurethane and are already localized or widely manufactured, and the present invention is not limited thereto. When the amount of the catalyst used in the curing agent portion is less than 0.01% by weight based on the total amount of the curing agent portion, it is impossible to achieve a sufficient curing rate and curing effect, so that curing time may be slow and there may be problems in commercialization, on the contrary, 3 weight If the amount is more than%, the amount of the catalyst used increases to form a high cost cost, and in view of the use of the product, excessive cost may not be suitable for commercialization.

The prepolymer main portion: the curing agent portion is made by mixing in a ratio of 0.5 to 2: 1 by weight ratio. When the prepolymer main part is used in an amount less than 0.5 part by weight based on 1 part by weight of the hardener, there may be a problem that the polymerized basic physical property tensile strength and elongation of the prepolymer main part are difficult to be properly expressed, on the contrary, exceeding 2 parts by weight. In this case, there is a problem of difficulty in the implementation of color due to the restriction of the use of the curing agent, decrease in the flowability of the curing agent due to the use of an excessive amount of pigment due to the implementation of the color, increase of the amount of catalyst due to the slowing of the curing time due to pigment interference. Can be.

The pigment may be selected from the group consisting of titanium dioxide, iron oxide, organic pigments and mixtures of two or more thereof.

The hardness after curing of the polyurethane resin obtained by the above-described configuration features can obtain a coating film having a high hardness within the range of 70 to 100 on the basis of Shore hardness A type.

The prepolymer of the prepolymer main portion preferably has a number average molecular weight within the range of 5,000 to 30,000. When the number average molecular weight of the prepolymer is less than 5,000, there may be a problem that the mechanical properties, that is, tensile strength and elongation is lowered, on the contrary, if the number average molecular weight exceeds 30,000, there is a problem that the commercialization of the product is difficult due to excessive viscosity have.

Especially thermosetting two-component polyurethane road lanes according to the present invention The higher the amount of the low equivalent polyol used based on the total amount of the prepolymer main part and the hardener part in the manufacture of the display paint, the faster the polyurethane resin is cured by the reaction between the prepolymer main part and the hardener part. There is a characteristic. This is because the lower the polyol equivalent weight, the smaller the number average molecular weight. From the point of view of the reaction kinetics, the polyol having the smaller number average molecular weight is faster due to the faster behavior, which increases the density of small molecules in the structure. Since the calorific value per unit amount is increased, the curing rate can be increased by the chain reaction. The present invention applies to this theory but is not intended to be bound thereto.

Preferably, the curing agent part further comprises polyoxyethylene glycol having a number average molecular weight of 200 to 400 in an amount within the range of 0.5 to 3% by weight based on the total weight of the curing agent part. The primary reaction rate between the prepolymer main portion and the hardener portion is heat, catalyst, moisture, and molecular structure, thereby accelerating the role of polyoxyethylene glycol, i.e., the onset of reaction heat starts with the prepolymer main portion and the polyoxy. Ethylene glycol is initiated by an exothermic reaction with a catalyst to induce a chain reaction, and before this reaction, at room temperature, the polyoxyethylene glycol contains moisture by combining with moisture, which is the residual isocyanate and the first catalyst and solar heat, that is, ultraviolet ( Reaction preferentially by UV), and the reaction is completed by providing heat above the energy level sufficient for the polyol of the other curing agent portion to react. For this reason, it can be understood that the ratio of residual isonate after bonding between the prepolymer main unit and the curing agent unit remains in the range of about 1.25 to 1.45 wt%, so as to be included in raw materials or to prepare for operation in a humid atmosphere. have. When the polyoxyethylene glycol is used in less than 0.5% by weight based on the total weight of the curing agent portion, there may be a problem that causes the use of expensive catalysts, resulting in a cost problem, on the contrary more than 3% by weight In this case, there may be a problem that excessive moisture contained by bonding with moisture at room temperature causes the liquid ratio to be defective, causing stickiness.

Thermosetting two-component polyurethane road lanes according to the present invention In addition to the prepolymer main portion, the hardener portion and the pigment, the display paint further includes additives used in the production of conventional polyurethane resins such as inorganic fillers, antifoaming agents, antifoaming agents, antisettling agents, sunscreen agents, color stabilizers, and the like. can do.

The thermosetting two-component polyurethane road lane marking paint according to the present invention having the above-described configuration is hard in the production of the prepolymer main part by reaction of polyisocyanate and polyol in the production of the polyurethane resin constituting the solid content. Isocyanates constituting the hard segment and polyols connected between them to form a soft segment, in particular, can be used to slow down the curing rate by controlling the use ratio of high equivalents and polymer polyols as polyols. In addition, it can be adjusted to increase the tensile elongation by increasing the length of the soft segment, and on the contrary, by controlling the ratio of the low-molecular weight polyol as the polyol as the polyol, the curing rate can be adjusted and the hardness can be adjusted. There is a characteristic.

In addition, by generating a low molecular weight polyoxyalkylene having a number average molecular weight of 200 to 400 in accordance with the present invention and by the control of the amount of the polyoxyalkylene generation of reaction heat through the chain reaction of single molecules and reaction It is possible to provide a thermosetting two-component polyurethane road lane marking paint based on a room temperature curing type polyurethane resin which can complete the curing reaction within a few minutes to several hours by promoting the above-mentioned. By shortening the air, speedy road maintenance is possible, and the effect of reducing traffic jams can be expected by simplifying the equipment.

In addition, according to the present invention, the polyol constituting the prepolymer is used to control the amount of low equivalent polyol in the polyol constituting the prepolymer, and at the same time as a polyol of the hardener portion reacting with the main portion of the prepolymer, a trifunctional group or smaller small average molecular weight The use of polyols (low equivalent polyols) has the advantage that the hardness can be increased in addition to the original elongation and tensile strength among the mechanical properties, and maximizes mechanical properties without using polycyclic hydrocarbons to increase the tensile and elongation rates. There is an advantage to this.

In addition, by using a low molecular weight polyoxyethylene ethylene oxide with a number average of 200 to 400 in the curing agent portion, it can be cured at high speed without using a harmful catalyst such as a large amount of lead catalyst, thereby allowing construction in winter. In order to be useful in actual application, the viscosity of the prepolymer main part and the hardener part may be easily fluidized when the main part and the hardener are mechanically mixed without flowing the main part and the hardener so that the viscosity can be easily adjusted to form a discharge coating film.

In addition, the thermosetting two-component polyurethane road lane according to the present invention The manufacturing method of the display paint is a thermosetting two-component polyurethane road lane comprising a prepolymer main portion and a curing agent portion. In the preparation of the display paint, (1) 5 to 31% by weight of the high equivalent polyol, 5 to 60% by weight of the low equivalent polyol and the remaining amount of the polyisocyanate are polymerized so that the content of unreacted free isocyanate is 9 to 20% by weight. A main part manufacturing step of preparing a prepolymer; (2) 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance A curing agent part manufacturing step of mixing the pigment to prepare a curing agent part; And (3) the prepolymer main portion: a packaging step of packaging at a ratio of 0.5 to 2: 1 by weight ratio of the curing agent portion.

The main part preparation step of (1) is a prepolymer having 5 to 31% by weight of a high equivalent polyol, 5 to 60% by weight of a low equivalent polyol and a residual amount to polymerize the polyisocyanate to have a content of unreacted free isocyanate of 9 to 20% by weight. It is made to prepare. The components used in this subject-manufacturing step and the mixing ratios thereof are the same or similar to those described above, and thus repeated descriptions will be avoided for the sake of brevity of the specification.

The curing agent part manufacturing step of (2) is a catalyst of 0.01 to 3% by weight, low equivalent polyol 30 to 65% by weight, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, additives 1 to 30 It consists of mixing a pigment as weight% and remainder and manufacturing a hardening | curing agent part.

The packaging step of (3) consists of packaging in a ratio of 0.5 to 2: 1 by weight ratio of the prepolymer main portion: the curing agent portion, which is mixed with the prepolymer main portion and the curing agent portion in the actual field immediately thermosetting two-component poly Functions as a urethane lane marking paint.

Hereinafter, the present invention will be described in detail with reference to examples.

The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

Example  One

Table 1 shows the composition of the main portion of the prepolymer, and Table 2 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One GP-700 100.00 233.33 3 28.50 2 GP-3000 100.00 1,000.00 3 28.50 3 TDI 151.20 87.00 2 43.00 Sum - 351.20 - - 100 Unreacted isocyanate = 14.46%
GP-700 = trifunctional product having a number average molecular weight of 700 obtained by adding propylene to glycerin, product name of KPX Chemical Co., Ltd., Korea
GP-3000 = trifunctional product having a number average molecular weight of 3000 obtained by adding propylene to glycerin, product name of KPX Chemical Co., Ltd., Korea
TDI = Toluene diisocyanate, product name of KPX Fine Chemicals Co., Ltd. in Korea

The viscosity of the prepolymer moiety was found to reach 3200 cps (25 ° C.).

division Product Name input Average equivalent weight percentage(%) One PP-400 196.00 200 55.81 2 PEG-200 5.00 100 1.42 3 TiO ₂ 127.00 - 36.16 4 T-9 3.00 - 0.85 5 33LV 3.00 - 0.85 6 Sedimentation inhibitors 3.00 - 0.85 7 Ultraviolet stabilizer 0.10 - 0.03 8 Antifoam 2.00 - 0.57 9 Bubble inhibitor 12.10 - 3.46 Sum - 351.20 - 100 PP-400 = bifunctional product having a number average molecular weight of 400 obtained by adding propylene oxide to dipropylene glycol, product name of KPX Chemical Co., Ltd., Korea
PEG-200 = Polyoxyethylene glycol, a bifunctional group product having a number average molecular weight of 200, a product name of KPX Green Chemical Co., Ltd.
TiO ₂ = titanium dioxide, used as a pigment
T-9 = a type of stannous octoate, product name of Air Products and Chemicals, Inc. in the United States of America T-9
33LV = product of the amine catalyst, product name Dabco33LV of Air Products & Chemicals, Inc.

When the prepolymer main part and the hardener were mixed in a ratio of 1: 1, curing was completed within 3 minutes at 25 ° C., and the hardness after curing was Shore A hardness 80.

Example  2

Table 3 below shows the composition of the main portion of the prepolymer, and Table 4 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One GP-700 180.00 233.33 3 42.20 2 GP-3000 21.50 1,000 3 5.04 3 TDI 225.00 87 2 52.76 Sum - 426.50 - - 100  Unreacted isocyanate = 17.66%

The viscosity of the prepolymer moiety was found to reach 7900 cps (25 ° C.).

division Product Name input Average equivalent weight percentage(%) One PP-200 51.00 100 15.36 2 PP-400 170.00 200 51.20 3 PEG-200 6.00 100 1.81 4 TiO ₂ 63.00 - 18.98 5 T-9 0.50 - 0.15 6 33LV 0.50 - 0.15 7 Sedimentation inhibitors 2.00 - 0.60 8 Ultraviolet stabilizer 0.50 - 0.15 9 Antifoam 8.50 - 2.56 10 Bubble inhibitor 30.00 - 9.04 Sum - 332.00 - 100  PP-200 = bifunctional product having a number average molecular weight of 200 obtained by adding propylene oxide to dipropylene glycol, product name of KPX Chemical Co., Ltd., Korea

When the prepolymer main portion and the curing agent portion were blended and applied at 0.62: 1, the curing was completed within 1 minute at 25 ° C, and the hardness after curing was Shore A hardness 93. However, when the viscosity of the prepolymer main portion reached 7900 cps (25 ° C.) and exceeded the range in this example, it was confirmed that the viscosity was too high to imply that mixing and application may be difficult. The physical properties of the obtained coating film were very hard and the elongation was only 3%.

Example  3

Table 5 shows the composition of the main portion of the prepolymer, and Table 6 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One GP-700 48.00 233.33 3 5.03 2 GP-3000 286.40 1,000 3 30.01 3 TDI 105.00 87 2 11.00 4 MDI 515.00 143 2 53.96 Sum - 954.40 - - 100 Unreacted isocyanate = 18.99%
MDI = methylene diphenyl diisocyanate, product name M-100 of Kumho Mitsui Corporation in South Korea

division Product Name input Average equivalent weight percentage(%) One PP-400 710.00 200 54.62 2 PEG-200 25.00 100 1.92 3 TiO ₂ 410.00 - 31.54 4 T-9 17.00 - 1.31 5 33LV 21.00 - 1.61 6 Sedimentation inhibitors 10.00 - 0.77 7 Ultraviolet stabilizer 3.00 - 0.23 8 Antifoam 30.00 - 2.31 9 Bubble inhibitor 74.00 - 5.69 Sum - 1300.00 - 100

When the prepolymer main part and the curing agent part were blended and applied at 0.73: 1, curing was completed within 5 minutes at 25 ° C., and the hardness after curing was Shore A hardness 72. It can be seen that the above hardness is in the limit of the measurement error range 3 of hardness, that is, when more polyols of high equivalent weight are applied, it may be difficult to commercialize due to the low hardness.

Example  4

Table 7 shows the composition of the main portion of the prepolymer, and Table 8 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One GP-700 84.50 233.33 3 29.97 2 GP-3000 14.50 1,000.00 3 5.14 3 TDI 23.10 87.00 2 8.19 4 MDI 159.90 143.00 2 56.70 Sum - 282.00 - - 100  Unreacted isocyanate = 15.0%, product name M-100 of Kumho Mitsui Corporation, Korea

division Product Name input Average equivalent weight percentage(%) One PP-400 158.00 200 52.27 2 PEG-200 4.00 100 1.32 3 TiO ₂ 110.60 - 36.59 4 T-9 0.90 - 0.30 5 33LV 1.20 - 0.40 6 Sedimentation inhibitors 4.70 - 1.55 7 Ultraviolet stabilizer 0.80 - 0.26 8 Antifoam 3.10 - 1.02 9 Bubble inhibitor 19.00 - 6.29 Sum - 302.30 - 100

When the prepolymer main portion and the curing agent portion were combined and applied to 0.93: 1, curing was completed within 20 seconds at 25 ° C., and the hardness after curing was Shore A hardness 91. However, when the viscosity of the prepolymer main portion reaches 7800 cps (25 ° C.) and exceeds the range in this example, it could be confirmed that the viscosity is too high to imply that mixing and application may be difficult.

Example  5

Table 9 shows the composition of the prepolymer main portion and Table 10 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One GP-700 100.00 233.33 3 25.13 2 GP-3000 100.00 1,000.00 3 25.13 3 MDI 198.00 143.00 2 49.74 Sum - 398.00 - - 100  Unreacted isocyanate = 9.03%

division Product Name input Average equivalent weight percentage(%) One PP-200 30.00 100 12.17 2 PP-400 62.00 200 25.15 3 PEG-200 5.00 100 2.03 4 TiO ₂ 125.00 - 50.71 5 T-9 3.00 - 1.22 6 33LV 4.00 - 1.62 7 Sedimentation inhibitors 3.00 - 1.22 8 Ultraviolet stabilizer 0.50 - 0.20 9 Antifoam 2.00 - 0.81 10 Bubble inhibitor 12.00 - 4.87 Sum - 246.50 - 100

When the prepolymer main portion and the curing agent portion were applied in a ratio of 1.6: 1, the curing was completed within 5 minutes at 25 ° C., and the hardness after curing was Shore A hardness 73. Problems of high viscosity (7800 cps) and low hardness, high usage ratio of the prepolymer main part, and high specific gravity of the pigment in the hardener part, resulting in low fluidity, and thus, may be an undesirable paint composition when outside the above range. Could confirm. In particular, a low equivalent PP-200 is used in the curing agent in order to bring the content of free isocyanate to a Shore A hardness of 70 or less within the reference value near the lower limit of the present invention, and the number average reference high molecular weight in the prepolymer main portion. Polymeric MDI (MDI) of the hardness can be maximized, but the hardness was 73. In addition, TDI was used together to improve viscosity, and thus, the hardness was decreased.

Example  6

Table 11 shows the composition of the main portion of the prepolymer, and Table 12 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One PP-200 84.50 100.00 2 28.60 2 GP-3000 20.00 1,000.00 3 6.77 3 TDI 191.00 87.00 2 64.63 Sum - 295.50 - - 100  Unreacted isocyanate = 18.91%

division Product Name input Average equivalent weight percentage(%) One PP-200 56.00 100 20.20 2 PP-400 112.00 200 40.41 3 PEG-200 5.60 100 2.02 4 TiO ₂ 78.40 - 28.28 5 T-9 2.24 - 0.81 6 33LV 3.36 - 1.21 7 Sedimentation inhibitors 3.36 - 1.21 8 Ultraviolet stabilizer 0.56 - 0.20 9 Antifoam 2.24 - 0.81 10 Bubble inhibitor 13.44 - 4.85 Sum - 277.20 - 100

When the prepolymer main portion and the curing agent portion were combined and applied at 1.07: 1, curing was completed within 15 seconds at 25 ° C., and the hardness after curing was found to be Shore A hardness 87. However, the viscosity of the main portion of the prepolymer is due to the low number average molecular weight polyol of the lower limit of When it reached 7800 cps (25 ° C.) and exceeded the range in this example, it could be confirmed that the viscosity was too high, suggesting that mixing and application may be difficult.

Example  7

Table 13 shows the composition of the prepolymer main portion and Table 14 shows the composition of the curing agent portion.

division Product Name input Average equivalent weight Number of functional groups percentage(%) One PP-200 28.00 100.00 2 5.43 2 GP-3000 100.00 1,000.00 3 19.38 3 MDI 388.00 143.00 2 75.19 Sum - 516.00 - - 100  Unreacted isocyanate = 18.99%

division Product Name input Average equivalent weight percentage(%) One PP-200 195.00 100 45.94 2 PP-400 20.00 200 4.71 3 PEG-200 5.00 100 1.18 4 TiO ₂ 170.00 - 40.05 5 T-9 6.00 - 1.41 6 33LV 6.00 - 1.41 7 Sedimentation inhibitors 8.00 - 1.88 8 Ultraviolet stabilizer 0.50 - 0.12 9 Antifoam 2.00 - 0.47 10 Bubble inhibitor 12.00 - 2.83 Sum - 424.50 - 100

When the prepolymer main portion and the curing agent portion were combined and applied at 1.22: 1, curing was completed within 5 minutes at 25 ° C., and the hardness after curing was Shore A hardness 72. Although the viscosity and hardness are somewhat low, it could be confirmed that the present invention exhibits the intended physical properties, and in the case of exceeding the above amount, in particular, the higher the polyol of the high equivalent weight, the lower the hardness of inappropriate physical properties. It could be confirmed that this can be obtained.

Example  8

The same procedure as in Example 7 was carried out except that MDI was replaced with TDI in the prepolymer main portion, and the viscosity of the prepolymer main portion was 1400 cps, and the prepolymer main portion and the hardener portion were 1.22: 1. When it mix | blended and applied, hardening was completed within 5 minutes at 25 degreeC, and the hardness after hardening was Shore A hardness 65. Although the viscosity and hardness were somewhat low, it could be confirmed that the present invention exhibited the intended physical properties, and when the amount was exceeded, it could be confirmed that implying that an inappropriate polyurethane material could be obtained. .

Industrial Applicability The present invention can be used in the industry for manufacturing road lane marking paint, and in the industry for maintaining roads using the same.

Claims (6)

A prepolymer major portion and a hardener portion; Wherein the prepolymer main portion is 5 to 31% by weight of high equivalent polyol, 5 to 60% by weight of low equivalent polyol And a content of 9 to 20% by weight of the unreacted free isocyanate obtained by polymerizing the polyisocyanate as the remainder; The hardener is 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance Including; The mixing ratio of the prepolymer main portion: the curing agent portion is made by mixing in a weight ratio of 0.5 to 2: 1, wherein the low equivalent polyol has an equivalent within the range of 100 to 277, the high equivalent polyol is within the range of 330 to 6,000 Thermosetting two-component polyurethane road lane marking paint, characterized in that having an equivalent. The method of claim 1,
The prepolymer main part of the prepolymer, the number average molecular weight is within the range of 5,000 to 30,000, the thermosetting two-component polyurethane road lane marking paint. delete The method of claim 1,
The thermosetting two-component polyurethane road lane marking paint, wherein the catalyst constituting the hardener portion is an amine catalyst or a tin catalyst or a mixture thereof. The method of claim 1,
The additive is a thermosetting two-component polyurethane road lane marking paint, characterized in that selected from the group consisting of anti-settling agent, anti-foaming agent, anti-foaming agent, sunscreen, color stabilizer and a mixture of two or more thereof. In the manufacture of a road lane marking paint comprising a prepolymer main portion and a hardener portion,
(1) a main part manufacturing step of preparing a prepolymer having a content of 5 to 31% by weight of a high equivalent polyol, 5 to 60% by weight of a low equivalent polyol and a residual amount to polymerize the polyisocyanate with a content of 9 to 20% by weight of the unreacted free isocyanate; ;
(2) 0.01 to 3% by weight of catalyst, 30 to 65% by weight of low equivalent polyol, 0.5 to 3% by weight of polyoxyethylene glycol having a number average molecular weight of 200 to 400 as a curing accelerator, 1 to 30% by weight of additives and the balance A curing agent part manufacturing step of mixing the pigment to prepare a curing agent part; And
(3) a packaging step of packing at a ratio of 0.5 to 2: 1 by weight of the prepolymer main portion: the curing agent portion;
It comprises a, wherein the low equivalent polyol has an equivalent in the range of 100 to 277, the high equivalent polyol has a equivalent in the range of 330 to 6,000, the thermosetting two-component polyurethane road lane display Method for the preparation of paints for use.