KR102366318B1 - Thermoplastic polyester resin used as a binder for road marking paints and as a binder for anti-slip agents, and a method for manufacturing the same - Google Patents

Abstract

The thermoplastic polyester resin used as a binder for the paint for road lane marking and the anti-slip agent according to the present invention is 100 parts by weight of an acid containing at least one selected from dicarboxylic acid, unsaturated fatty acid, and monoacid and at least two alcohol groups Aliphatic alcohol 100 including at least one selected from glycerin, pentaerythritol, 1,4-butadiol, 1,5-pentadiol, 1,6-hexadiol, catechol, dopamine, and resorcinol to 200 parts by weight, wherein the dicarboxylic acid comprises at least one selected from oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, server acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, and sebacic acid, , The monoacid includes at least one selected from myristic acid, palmitic acid, stearic acid and tall oil fatty acid, and the unsaturated fatty acid is crotonic acid, myristoleic acid, palmitoleic acid oleic acid, elaidic acid, maleic acid, It is characterized in that it contains any one or more selected from fumaric acid.
In addition, according to the present invention, in the method for producing a thermoplastic polyester resin, 100 parts by weight of an acid and 100 to 200 parts by weight of an alcohol are added to a reaction tank to prepare a mixture, and the mixture is heated to 150 to 230° C. to generate water. The first step of obtaining a primary product in an oligomeric state by flowing out the second step of raising the temperature of the reactant to a temperature of about 240 to 260 ° C. While maintaining the vacuum degree of the reaction tank within the range of 0.01 to 2 torr, hot melt of the polyester resin It is characterized in that it includes a third step of obtaining

Description

The thermoplastic polyester resin used as a binder for road marking paints and as a binder for anti-slip agents, and a method for manufacturing the same}

The present invention relates to a thermoplastic polyester resin used as a binder in the manufacture of road marking paints and anti-slip agents, and a method for manufacturing the same, and more particularly, as a construction binder by a heat-sealing method of paints for marking paints and anti-slip agents. It relates to a polyester resin having a solid form in the form of hot melt beads and a method for manufacturing the same.

Due to the development of means of transportation, especially the development and dissemination of automobiles, roads have become more numerous, wider, and more complex.

Accordingly, there is a need for more information to be transmitted to the driver from the road surface in the operation of the vehicle, and information on the destination on the speed limit and the direction of travel is applied directly on the road surface and displayed in letters or figures, Various types of paints for road signs used for information on the direction of travel on the road and information for crosswalks have been developed and used.

In particular, in special areas where danger exists, such as bus lanes, child protection zones, road slippage, slopes, or in front of schools, the road surfaces are painted in various forms to enhance driver visibility.

In addition, the paints used at this time can be largely divided into oil-based road marking paints, water-based road marking paints, fusion-type road marking paints, and the like according to raw material components and construction methods.

Here, the oil-based paint is prepared in a liquid phase after properly mixing an organic solvent and a pigment with an acrylic or alkyd resin. Water-based paints are manufactured in liquid form by mixing pigments with emulsion resins, so construction is limited and drying is slow. In addition, the oil-based paints and water-based paints are worn after the solvent and water are dried and the thickness of the paint becomes thin. There is also the downside of having fewer floors.

On the other hand, the fusion coating material is manufactured in powder form by mixing pigments, fillers and glass beads with a thermoplastic resin, and is a solvent-free lane display material supplied in lumps, granules or powder form as a paint used by thermal melting during construction. say

When the powder is melted by applying heat through a specific processing device and then constructed, there are few restrictions on the thickness of the coating at the time of road marking, and it is possible to pass immediately after cooling during construction.

Currently, petroleum resins (isoprene, piperylene, 2-methylbutene, etc.) are mainly used as thermoplastic resins for fusion-type road marking paints. Polyethylene wax, phthalate plasticizers such as di-2-ethylhexyl phthalate, calcium carbonate , glass beads, UV stabilizer, titanium dioxide, EVA, etc. are used as additional ingredients.

However, the conventional heat-sealing road marking paints containing the petroleum-based resin as a main component emit a bad odor during construction, causing discomfort, cracks easily occur and are weak in strength, and have weak heat resistance and weather resistance. Therefore, the improvement of durability is requested|required.

KR 10-0866067 B1 'Binder for paint and paint comprising same'

The present invention has been devised to solve the above problems, and provides ease of construction by removing bad odors during construction of road marking paints and anti-slip agents, and by strengthening strength, heat resistance and weather resistance, durability of road signs An object of the present invention is to provide a thermoplastic polyester resin that can be used as a binder for road marking paint and an anti-slip agent that can maintain a brightly colored lane for a long time by improving it, and a method for manufacturing the same.

The thermoplastic polyester resin used as the binder of the road lane marking paint and the binder of the anti-slip agent according to the present invention contains 100 parts by weight of an acid and alcohol containing at least one compound selected from dicarboxylic acid, unsaturated fatty acid, and monoacid. contains at least two groups and is selected from the group consisting of glycerin, pentaerythritol, 1,4-butadiol, 1,5-pentadiol, 1,6-hexadiol, catechol, dopamine, resorcinol, and combinations thereof 100 to 200 parts by weight of an aliphatic alcohol containing at least one compound, wherein the dicarboxylic acid is oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, server acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid , at least one compound selected from the group consisting of sebacic acid and combinations thereof, wherein the monoacid is at least one selected from the group consisting of myristic acid, palmitic acid, stearic acid and tall oil fatty acids and combinations thereof. It comprises the above compounds, wherein the unsaturated fatty acids include at least one compound selected from the group consisting of crotonic acid, myristoleic acid, palmitoleic acid, elaidic acid, maleic acid, fumaric acid, and combinations thereof. do it with

More specifically, the acid is, with respect to 100 parts by weight of the acid, 70 to 90 parts by weight of the dicarboxylic acid, and 100 parts by weight of the acid, the content of 10 to 30 parts by weight of the unsaturated fatty acid and the monoacid It is characterized in that it is 20 parts by weight or less.

More specifically, the thermoplastic polyester resin is characterized in that the molar ratio of the acid and the alcohol satisfies 1:1.1 to 1.5, and the resin acid value of the thermoplastic polyester resin is 10 mgKOH/g or less.

And, in the method for producing a thermoplastic polyester resin used as a binder for the paint for road lane marking and the anti-slip agent of the present invention, 100 parts by weight of an acid and 100 to 200 parts by weight of an alcohol are added to a reaction tank, and then, the mixture is heated at 150° C. A first step of separating water generated during the preparation of the mixture by heating to a temperature of 230° C. to obtain a primary product in an oligomeric state, and after the first step, the oligomeric state obtained through the first step After the second step and the second step of raising the temperature of the reactant to a temperature of 240 to 260 ° C., while maintaining the vacuum degree of the reaction tank at a vacuum degree of 0.01 torr to 2 torr, to produce a hot melt composition of the polyester resin and a third step.

More specifically, in the first step, when preparing the mixture, the mixture is prepared so that the molar ratio of the acid and the alcohol is 1: 1.1 to 1.5, and the resin acid value is 10 mgKOH/g or less. characterized.

The present invention provides a thermoplastic polyester resin that can be used as a construction binder by a heat fusion method for paints for display paints and anti-slip agents, but provides higher strength, heat resistance and weather resistance than conventional petroleum resin binders, thereby improving durability By doing so, it has excellent adhesion to road lanes and has the effect of exhibiting excellent performance when applied as a binder for road marking paints and anti-slip agents by maintaining bright colors and luster for a long period of time.

In addition, by using the polyester resin of the present invention instead of the petroleum resin binder, it is possible to provide an effect of improving the easiness of construction by removing a foul odor during construction.

1 is a flowchart illustrating a process for producing a thermoplastic polyester resin used as a binder for road marking paint and a binder for an anti-slip agent according to the present invention.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings.

However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and are common in the art to which the present invention pertains. It is provided to fully inform those with knowledge of the scope of the invention, and the present invention is only defined by the scope of the claims.

In addition, the terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention.

In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of elements other than those mentioned.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs.

Hereinafter, a thermoplastic polyester resin used as a binder for road marking paint and a binder for an anti-slip agent according to the present invention and a method for manufacturing the same will be described in detail.

However, the present invention is not limited to the following examples and may be implemented in other forms. The embodiments introduced herein are provided so that the published content can be more complete and the spirit and features of the present invention can be sufficiently conveyed to those skilled in the art.

The present invention is composed of 100 parts by weight of an acid and 100 to 200 parts by weight of an alcohol, wherein the molar ratio of the acid and the alcohol satisfies 1:1.1 to 1.5, and at the same time the resin acid value of 10 mgKOH/g or less. It features a thermoplastic polyester resin used as a binder.

Previously, in order to make a thermoplastic polyester resin used as a binder for road marking paint and a binder for an anti-slip agent according to the present invention, the above-described condensation reaction of dicarboxylic acid and polyhydric alcohol is performed, of which dicarboxylic acid The type and content of it can be designed according to the desired physical properties.

In addition, the flexibility, drying time, and adhesive strength of the binder possessed by the binder when constructing the road marking paint and the anti-slip agent may act as very important factors.

Here, as the time for the road marking paint and the anti-slip agent to solidify differently depending on the characteristics of the resin serving as a binder during thermal fusion construction on the road surface of the road marking paint and the anti-slip agent, as the binder The properties of the resin used may greatly affect the construction time of the road marking paint and the anti-slip agent.

First, the acid includes at least one of a dicarboxylic acid and a mono acid and an unsaturated fatty acid.

Here, the dicarboxylic acid includes at least one compound selected from oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, server acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, and sebacic acid.

And, the monoacid includes at least one compound selected from myristic acid, palmitic acid, stearic acid, and tall oil fatty acid.

In addition, the unsaturated fatty acid is characterized in that it comprises at least one selected from crotonic acid, myristoleic acid, palmitoleic acid oleic acid, elaidic acid, maleic acid, and fumaric acid.

More specifically, with respect to 100 parts by weight of the acid, 70 to 90 parts by weight of the dicarboxylic acid, 20 parts by weight or less of the monoacid and 10 to 30 parts by weight of the unsaturated fatty acid may be included.

That is, with respect to 100 parts by weight of the acid, 70 parts by weight of the dicarboxylic acid and 30 parts by weight of the unsaturated fatty acid may be used, or 75 parts by weight of the dicarboxylic acid, 5 parts by weight of the mono acid and 20 parts by weight of the unsaturated fatty acid may be used. It can be carried out in various combinations so that

Here, the dicarboxylic acid may be an aromatic dicarboxylic acid.

And, in order to make a thermoplastic polyester resin used as a binder for road marking paint and a binder for an anti-slip agent according to the present invention, the above-described condensation reaction of dicarboxylic acid and polyhydric alcohol is performed, of which dicarboxylic acid The type and content of it can be designed according to the desired physical properties.

In addition, when the thermoplastic polyester resin according to the present invention is manufactured, the drying time of the road marking paint and the anti-slip agent using the thermoplastic polyester as a binder can be adjusted by controlling the content of dicarboxylic acid.

More specifically, with respect to 100 parts by weight of the acid prepared to prepare the thermoplastic polyester resin, when the content of the dicarboxylic acid is less than 70 parts by weight, the drying time of the finally manufactured thermoplastic polyester resin As this excessive increase, a significant problem may occur in the workability of the above-described road marking paint and anti-slip agent.

And, when the content of the aromatic dicarboxylic acid exceeds 90 parts by weight with respect to 100 parts by weight of the acid, the strength of the finally produced thermoplastic polyester resin is excessively increased, so the binder of the road marking paint There may be problems that make it impossible to apply as a .

Here, when the content of the aromatic dicarboxylic acid increases within the above-described range, the strength of the finally produced thermoplastic polyester increases according to the properties possessed by the aromatic dicarboxylic acid, and the drying time is shortened to provide quick drying properties. .

Next, by controlling the addition amount of the mono acid, it is possible to control the viscosity of the polyester resin. At this time, as the mono acid is added, the molecular weight of the finally produced thermoplastic polyester resin is lowered and the viscosity is also lowered.

Here, when the mono acid is added in excess of 20 parts by weight based on 100 parts by weight of the acid, the viscosity of the finally produced thermoplastic polyester resin is excessively lowered, so that the binder and the anti-slip agent of the road marking paint are A problem in which the viscosity as a binder is not satisfied may occur.

In addition, in order to control the flexibility of the polyester resin, the content of unsaturated fatty acids may be adjusted.

Here, with respect to 100 parts by weight of the acid, when less than 10 parts by weight of the unsaturated fatty acid is added, as the flexibility of the finally produced thermoplastic polyester resin is excessively lowered, the thermoplastic polyester is applied from the road There may be a problem in that the road marking paint and the anti-slip agent may be easily peeled off.

And, with respect to 100 parts by weight of the acid, when the unsaturated fatty acid is added in excess of 30 parts by weight, as the flexibility of the finally produced thermoplastic polyester resin is excessively increased, the road marking paint and the anti-slip agent Problems that may deteriorate constructability may occur.

In addition, the alcohol contains two or more alcohol groups including glycerin, pentaerythritol, 1,4-butadiol, 1,5-pentadiol, 1,6-hexadiol, catechol, dopamine, resorcinol, etc. One or more of the fatty alcohols may be selected and mixed.

That is, based on 100 parts by weight of the alcohol, 50 parts by weight of the glycerin and 50 parts by weight of 1,4-butadiol are mixed and used, or 50 parts by weight of the glycerin and 50 parts by weight of the 1,6-hexadiol are mixed and used. Alternatively, 50 parts by weight of the pentaerythritol and 50 parts by weight of 1,4-butadiol are used, or 50 parts by weight of the pentaerythritol and 50 parts by weight of the 1,6-hexadiol are mixed and used. Do.

In addition, the thermoplastic polyester resin according to the present invention can improve the quality of not only dicarboxylic acid and polyhydric alcohol, but also a catalyst for smooth reaction progress between the dicarboxylic acid and polyhydric alcohol, and finally the thermoplastic polyester resin produced. It may further include an antioxidant that may be used.

The thermoplastic polyester resin of the present invention as described above is a product produced by the polycondensation reaction of various types of dicarboxylic acids and polyhydric alcohols, and the acid is one or more compounds selected from dicarboxylic acids, monoacids and unsaturated fatty acids. Including, the alcohol includes any one or more compounds selected from aliphatic alcohols containing two or more alcohol groups.

In addition, the thermoplastic polyester resin prepared to have the above composition is solid at room temperature, and has a softening point of 85° C. or higher. And, since the viscosity of the thermoplastic polyester resin is 500 to 1000 cps in the vicinity of 180° C. and has good fluidity, it has easy conditions for manufacturing paints and anti-slip materials.

Here, the softening point was measured by a standard Ring and Ball method according to ASTM E 28, and the viscosity was measured with a Brookfield viscometer.

Here, when mixing the thermoplastic polyester resin using the dicarboxylic acid and the aliphatic alcohol, the molar ratio of the acid and the alcohol is preferably 1:1.1 to 1.5, and as a result, a resin acid value of 10 mgKOH/g or less can be obtained there is.

At this time, when the resin acid value is higher than 10 mgKOH/g, a film with low alkali resistance is formed on the finally produced thermoplastic polyester resin, so that adhesion to the adherend, that is, adhesion to the road surface is inhibited.

Therefore, it is formulated to have a resin acid value of 10 mgKOH/g or less, but lowering the resin acid value to a range that does not impair adhesion with the adherend (road surface) improves alkali resistance, and consequently makes it more stable on the road surface can be adhered to.

Next, the description of the thermoplastic polyester resin used as the binder of the road marking paint and the binder of the anti-slip agent according to the present invention is finished. Hereinafter, a method for manufacturing the thermoplastic polyester resin will be described.

1 is a flowchart illustrating a process for producing a thermoplastic polyester resin used as a binder for road marking paint and a binder for an anti-slip agent according to the present invention.

Referring to Figure 1, the method for producing a thermoplastic polyester resin according to the present invention, a first step (S100) proceeding to obtain a primary product in an oligomeric state, a second step of raising the temperature of the primary product ( S200) and a third step (S300) of generating a hot melt composition, and each step will be described in more detail below.

First, in the first step, 100 parts by weight of an acid and 100 to 200 parts by weight of an alcohol are added to the reactor to prepare a mixture, and the mixture is heated to a temperature of 150 to 230° C. for a sufficient time to drain water to form an oligomeric state. to obtain the primary product of

Here, in the mixture, not only dicarboxylic acid and polyhydric alcohol, but also a catalyst for smooth reaction progress between the dicarboxylic acid and polyhydric alcohol, and an antioxidant capable of improving the quality of the finally produced thermoplastic polyester resin are added. may include

At this time, when the temperature of the mixture is less than 150 ℃, a problem occurs that the reaction rate of the mixture is slow, and when the temperature of the mixture exceeds 230 ℃, the mixture may be denatured.

In this case, the molar ratio of the acid to the alcohol is 1: 1.1 to 1.5, it is preferable to prepare a mixture having a resin acid value of 10 mgKOH/g or less.

At this time, a catalyst is used to promote the reaction between the acid and the alcohol, and the catalyst is a titanium-based catalyst comprising at least one catalyst selected from among titanium methoxide, titanium ethoxide, titanium isopropoxide, and titanium acetylacetonate. can be used

In this case, the amount of the catalyst may be added in an amount of 0.01 parts by weight to 0.09 parts by weight based on 100 parts by weight of the mixture.

Here, when the amount of the catalyst is less than 0.01 parts by weight, the reaction rate is significantly lowered, and when the amount of the catalyst exceeds 0.09 parts by weight, there is a problem that excessive cost may be generated.

More preferably, the amount of the catalyst used is 0.05 parts by weight of the catalyst based on 100 parts by weight of the mixture.

In addition, in order to prevent oxidation of the mixture during the reaction, nitrogen is filled in the reactor, and an appropriate amount of antioxidant is added.

Here, as the antioxidant, a cresol-based antioxidant (o, m, p-cresol, etc.) may be mainly used, and the antioxidant is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the mixture. can be

At this time, when less than 0.1 parts by weight of the antioxidant is added, the antioxidant performance effect of the thermoplastic polyester resin through the antioxidant is not sufficiently exhibited, and when the antioxidant is added in an amount exceeding 5 parts by weight, oxidation The reaction with nitrogen gas causes a problem of discoloration (yellowing) of the thermoplastic polyester resin as a final product.

And, the second step is a step of raising the temperature of the primary product in the oligomeric state prepared through the first step to a temperature of about 240 ~ 260 ℃.

In the third step, after the second step, the vacuum degree of the reaction tank is maintained at 0.01 torr to 2 torr, and the hot melt composition of the polyester resin having a predetermined viscosity is produced.

In particular, the third step is a step of finally obtaining a hot melt composition of a polyester resin while maintaining the vacuum degree described above by gradually applying a vacuum while taking care not to scatter the reactants when the condensation reaction is finished.

The hot melt composition of the polyester resin obtained in the third step has a melt viscosity of 500 to 100 cps (centipoise) measured at 180 ° C., and a softening point of 85 ° C. or higher. It is possible to obtain a thermoplastic polyester resin present in a solid state at room temperature .

The polyester resin having a solid form produced by the above manufacturing method can be used as a binder during construction by a heat fusion method of a paint for paint display and a road anti-slip agent.

Hereinafter, the present invention will be described in detail through examples, and is not limited to the examples described below.

[Example 1]

100 parts by weight of an acid mixed with 80 parts by weight of succinic acid (dicarboxylic acid), 20 parts by weight of stearic acid (mono acid) and 20 parts by weight of fumaric acid (unsaturated fatty acid), glycerin 50 parts by weight and 100 parts by weight of alcohol in which 50 parts by weight of 1,4-butadiol is mixed is put into a sealed 1000L reactor, and the reaction of the acid and alcohol mixture is proceeded while stirring.

Then, with respect to 100 parts by weight of the mixture of acid and alcohol, 0.1 parts by weight of a titanium isopropoxide catalyst as a catalyst is added, and then the mixture in which the catalyst is added is heated for a sufficient time at 200 to 220 ° C. to prepare a primary product of

After that, the temperature of the thus-prepared oligomeric primary product is raised to a temperature of about 240 to 260 ° C again, and when the condensation reaction is finished, a vacuum is gradually applied to solidify while maintaining a vacuum degree of 0.01 to 2 torr, A hot melt of polyester resin was prepared.

Thereafter, with respect to 100 parts by weight of the paint for paint display and the anti-slip agent, 18 parts by weight of the hot melt of the polyester resin prepared as described above, 5 parts by weight of wax and additives, and 77 parts by weight of lime powder were put into the reactor and stirred. Then, it was melted at 180 degrees and solidified to make a specimen.

[Example 2]

100 parts by weight of an acid in which 70 parts by weight of succinic acid (dicarboxylic acid), 30 parts by weight of stearic acid (mono acid) and 30 parts by weight of fumaric acid (unsaturated fatty acid) are mixed, 50 parts by weight of glycerin, and 100 parts by weight of alcohol mixed with 50 parts by weight of 1,6-hexadiol is put into a sealed 1000L reactor, and the reaction proceeds while stirring.

Then, with respect to 100 parts by weight of the mixture of acid and alcohol, 0.1 parts by weight of a titanium isopropoxide catalyst as a catalyst is added, and then the mixture in which the catalyst is added is heated for a sufficient time at 200 to 220 ° C. to prepare a primary product of

The temperature of the thus-prepared oligomeric primary product is again raised to a temperature of about 240°C to 260°C, and when the condensation reaction is finished, a vacuum is gradually applied to solidify while maintaining a vacuum degree of 0.01 torr to 2 torr, and finally poly A hot melt of ester resin was prepared.

Thereafter, with respect to 100 parts by weight of the paint for paint display and 100 parts by weight of the anti-slip agent, 18 parts by weight of the hot melt of the polyester resin prepared as described above, 5 parts by weight of wax and additives, and 77 parts by weight of lime powder were put into the reactor and stirred, It was melted at 180 degrees and solidified to make a specimen.

[Comparative example]

Comparative Example is provided so that the C5-based petroleum resin generated as a by-product in the naphtha decomposition process can be used as a binder for road marking paint and anti-slip agent.

Then, with respect to 100 parts by weight of the paint and anti-slip agent for paint display, 18 parts by weight of the C5-based petroleum resin, 5 parts by weight of wax and additives, and 77 parts by weight of lime powder were put into the reactor, stirred, and then melted and solidified at 180 degrees. made a psalm

[Table 1] below is a table of ultraviolet (UV) aging test results of paints and anti-slip agents to which the resin binders prepared according to various Examples 1 and 2 and Comparative Examples of the present invention are applied.

[Table 1]

The ultraviolet (UV) aging test of the paint for display and the anti-slip agent was performed according to KS M ISO 4892-3.

In addition, after the ultraviolet (UV) aging test was completed, the luminance rate and the luminance rate difference (Δβ) before and after ultraviolet (UV) aging were calculated by the luminance measurement method after taking it out and leaving it at room temperature for 1 hour, and 4 kinds of yellow paints According to the quality standard, the difference in luminance ratio (Δβ) should be less than or equal to 0.05.

As shown in [Table 1], in the case of Examples 1 and 2, in which the paint was prepared using a polyester binder, the difference in luminance ratio (Δβ) was higher compared to Comparative Example 1 in which the paint was prepared using a petroleum resin binder. As it was lower, it showed better weather resistance.

Each of the steps according to the present invention described above may be executed in a different order if necessary, and even in the case of an embodiment in which the order is changed in this way, it is natural that they fall within the scope of the present invention.

As described above, the present invention has been described with reference to Examples and Comparative Examples, but this is only for explaining the invention, and those of ordinary skill in the art to which the present invention pertains may obtain various modifications or equivalents from the detailed description of the invention. It will be appreciated that embodiments are possible.

Therefore, the true scope of the present invention should be determined by the technical spirit of the claims.

S100: Step 1
S200: second stage
S300: 3rd stage

Claims (5)

100 parts by weight of an acid including both dicarboxylic acid, unsaturated fatty acid and monoacid; and
contains at least two alcohol groups and is selected from the group consisting of glycerin, pentaerythritol, 1,4-butadiol, 1,5-pentadiol, 1,6-hexadiol, catechol, dopamine, resorcinol, and combinations thereof 100 to 200 parts by weight of an aliphatic alcohol containing at least any one or more compounds to be included;
The acid is
Based on 100 parts by weight of the acid, 70 to 80 parts by weight of the dicarboxylic acid; and
With respect to 100 parts by weight of the acid, 10 to 20 parts by weight of the unsaturated fatty acid;
Based on 100 parts by weight of the acid, the content of the monoacid is 20 parts by weight or less,
The dicarboxylic acid is
At least one compound selected from the group consisting of oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, serveric acid, azelaic acid, terephthalic acid, isophthalic acid, phthalic acid, sebacic acid, and combinations thereof,
The monoacid is
At least one compound selected from the group consisting of myristic acid, palmitic acid, stearic acid and tall oil fatty acids and combinations thereof,
The unsaturated fatty acids are
It contains at least one compound selected from the group consisting of crotonic acid, myristoleic acid, palmitoleic acid oleic acid, elaidic acid, maleic acid, fumaric acid, and combinations thereof,
A thermoplastic polyester resin used as a binder for road marking paint and an anti-skid agent, characterized in that the resin acid value is 10 mgKOH/g or less. delete delete In the method for producing a polyester resin,
In the method for producing the polyester resin, 100 parts by weight of an acid containing all of dicarboxylic acid, unsaturated fatty acid and monoacid and 100 to 200 parts by weight of an alcohol are added to a reaction tank to prepare a mixture in which an acid and an alcohol are mixed, The resin acid value of the mixture is prepared to have 10 mgKOH/g or less, and the mixture is heated to a temperature of 150 ° C. to 230 ° C. to separate water generated when the acid and alcohol are mixed to obtain a primary product in an oligomeric state. Level 1;
After the first step, a second step of raising the temperature of the primary product in the oligomeric state obtained through the first step to a temperature of 240 to 260 ℃; and
After the second step, a third step of maintaining a vacuum degree of 0.01 torr to 2 torr in the reaction tank to produce a hot melt composition of a polyester resin having viscosity;
When the first step proceeds,
The acid is
It contains a dicarboxylic acid and an unsaturated fatty acid, with respect to 100 parts by weight of the acid, 70 to 80 parts by weight of the dicarboxylic acid;
Based on 100 parts by weight of the acid, 10 to 20 parts by weight of the unsaturated fatty acid; and
A method for producing a thermoplastic polyester resin used as a binder for road marking paint and an anti-slip agent, characterized in that it contains 20 parts by weight or less of the monoacid with respect to 100 parts by weight of the acid. delete

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