KR20170003258A - Composition for traffic paint and preparing method thereof - Google Patents

Abstract

The present invention relates to a composition for traffic paint. More particularly, the present invention relates to a traffic paint composition having favorable abrasion resistance and compression strength while having excellent flowability by comprising a petroleum resin with improved color and specific gravity while having a narrow molecular weight distribution.

Description

TECHNICAL FIELD The present invention relates to a composition for a traffic paint,

The present invention relates to a composition for traffic paint, and more particularly, to a composition for traffic paint comprising a petroleum resin having an improved flowability and an improved specific gravity with good abrasion resistance and compressive strength.

C5-based petroleum resin is generally produced by catalytic condensation of oil produced in naphtha cracking process. It is produced by hot melt adhesive (hereinafter referred to as "HMA"), hot melt pressure sensitive adhesive (hereinafter referred to as "HMPSA" ), Road marking paint, and the like. Among these petroleum resin applications, HMA and HMPSA are developing various kinds of products as environment friendly points and adhesives in the form of solvent-free form, and high growth is expected in the future.

Among them, the traffic paint which displays the center line, the crosswalk, the speed limit display, the progress direction mark, the parking space line, etc. on the road surface of the asphalt, concrete, etc. is mainly used as rosin resin, rosin resin such as rosin, Polyester resins, and the like have been used. Of these, modified rosin-based resins such as maleinized rosin are most excellent. However, in the case of the modified rosin-based resin, since the raw material is dependent on natural products, the supply stability is lowered and the resin itself has a problem of smelling.

Therefore, a petroleum resin has been attracting attention instead of a modified rosin resin, and it is required not to be discolored even at a time of coating and a long time of coating. In order to ensure visibility of drivers, when beads are compounded, And it is also required that the viscosity be adjusted so that it can flow well on the road surface when sprayed.

Conventionally, in order to lower the viscosity of the traffic paint, the plasticizer has been increased or a low viscosity plasticizer has been used, but there have been problems such as environmental hazard and deterioration of stain resistance. In order to lower the viscosity, low molecular weight high density polyethylene is used in an increased amount. In this case, the heat distortion of the traffic paint is increased and the beads are easily sunk so that the visibility of the driver is insufficient and the strength is lowered.

The main object of the present invention is to provide a traffic paint composition having good compressive strength and abrasion resistance and excellent fluidity by using a petroleum resin having a low specific gravity.

In order to achieve the above object, the present invention provides a composition for traffic paint comprising a petroleum resin, calcium carbonate, glass beads, synthetic wax, plasticizer and inorganic pigment.

In a preferred embodiment of the present invention, the petroleum resin has a weight average molecular weight of 1,000 to 3,500 g / mol.

In a preferred embodiment of the present invention, the molecular weight distribution of the petroleum resin is 2.8 or less.

In a preferred embodiment of the present invention, the petroleum resin has a softening point of 93 to 97 占 폚

In a preferred embodiment of the present invention, the petroleum resin has a specific gravity of 0.96 or less.

In one preferred embodiment of the present invention, the acid value of the petroleum resin may be 2.5 to 2.9.

In a preferred embodiment of the present invention, the composition comprises 10 to 20% by weight of petroleum resin, 50 to 65% by weight of calcium carbonate, 15 to 20% of glass beads, 0.01 to 1% by weight of synthetic wax, 0.5 to 2% By weight and 2 to 6% by weight of an inorganic pigment.

In a preferred embodiment of the present invention, the petroleum resin is produced by reacting oil A, a molecular weight modifier, and a cyclic olefin-based monomer.

In a preferred embodiment of the present invention, the oil A and the molecular weight regulator are produced by reacting at a weight ratio of 50:25 to 45:20.

In a preferred embodiment of the present invention, the oil A is produced by heating the oil containing unsaturated hydrocarbons having 4 to 6 carbon atoms to remove the dimer and the dimer component.

In a preferred embodiment of the present invention, the molecular weight modifier is prepared by subjecting an oil containing unsaturated hydrocarbons having 4 to 6 carbon atoms to heat treatment to remove dimer and dimer components, followed by partial hydrogenation reaction by adding a hydrogenation catalyst . ≪ / RTI >

The paint composition according to the present invention contains a petroleum resin with improved molecular weight and specific gravity while having a narrow molecular weight distribution so that the viscosity can be controlled so that it can flow well on the road surface with good compressive strength and abrasion resistance and low flowability. Do.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In one aspect, the present invention provides a composition for a traffic paint comprising a petroleum resin, calcium carbonate, glass beads, synthetic wax, plasticizer and inorganic pigment.

Wherein the petroleum resin is a polymerization product of an oil A and a molecular weight regulator and the oil A is prepared by heating an oil containing an unsaturated hydrocarbon having 4 to 6 carbon atoms to remove a dimer and a dimer component, Heating the oil A to dimerize the cyclic conjugated diene compound contained in the oil A, distilling the oil A containing the dimeric cyclic conjugated diene compound to remove the dimerized cyclic conjugated diene compound Which is the product of the partial hydrogenation reaction.

The above-mentioned oil A is an initial raw material obtained by separating unsaturated hydrocarbons having 4 to 6 carbon atoms in a boiling point range of 20 to 60 占 폚 in oil fractions obtained by pyrolysis of petroleum such as naphtha and the like, and cyclopentadiene and methylcyclopentadiene A cyclic conjugated diene compound such as isoprene and 1,3-pentadiene, and the like. In addition, it is preferable that the cyclic conjugated diene compounds not only cause gel formation but also have a high molecular weight and deteriorate color, so that the content thereof is reduced to about 3% by weight or less in the initial raw material.

In order to remove the cyclic conjugated diene compound in the initial raw material, the initial raw material is heated. The heat treatment may be carried out at 100 to 200 ° C for 2 to 20 hours, preferably at 110 to 180 ° C for 4 to 8 hours in view of increasing the productivity while reducing the color deterioration factor. At this time, the cyclic conjugated diene compound is dimerized and the cyclized conjugated diene compound is a high boiling compound. Therefore, the cyclic conjugated diene compound is easily removed as a tower bottom component through a distillation process.

As described above, the oil A obtained by removing the dimer with the column bottom component and obtained from the column top is obtained by reacting a chain conjugated diene compound such as 1,3-pentadiene, isoprene, and the like with a monoene such as 1-pentene, . At this time, the content of the chain conjugated diene is about 20 to 40% by weight based on the total oil fraction. Particularly 10 to 20 parts by weight of 1,3-pentadiene, 10 to 20 parts by weight of isoprene, 5 to 10 parts by weight of pentene and 5 to 10 parts by weight of 2-methyl-2-butene.

In the oil A, the cyclic conjugated diene compound was removed from the components causing gel formation, but a chain conjugated diene compound such as isoprene or 1,3-pentadiene still remained. In this chain conjugated diene, gel production by isoprene is much larger than that by 1,3-pentadiene, and the increase of the average molecular weight and the molecular weight distribution is also significantly increased by isoprene. Therefore, among the chain conjugated diene compounds, The content should be as low as possible. However, since isoprene content is the most abundant in oil A, simply removing isoprene is not economical because the raw material loss is excessive.

Accordingly, in the present invention, the partial hydrogenation reaction of the oil A is carried out without any additional treatment to produce a molecular weight regulator capable of suppressing the formation of a gel during petroleum resin production and appropriately controlling the molecular weight. At this time, the partial hydrogenation reaction of the oil A is brought into contact with hydrogen while maintaining the total pressure and temperature in the presence of the hydrogenation catalyst.

That is, in the present invention, the molecular weight regulator is produced by adding a hydrogenation catalyst to oil A and performing partial hydrogenation reaction. Partially hydrogenated molecular weight regulators economically reduce the content of isoprene causing gel formation, so that when the petroleum resin is mixed with oil A, it is possible to prevent gel formation and to improve the color and specific gravity Can be produced.

That is, when the mixed petroleum resin is contained in the composition for a traffic paint, the compressibility and the wear resistance are good and the fluidity is low, so that uniform workability can be achieved at an appropriate speed, and workability can be improved.

The contents of the oil A and the molecular weight regulator are summarized in Table 1 below.

division Oil A (% by weight)
(A mixed oil in which a cyclic conjugated diene is removed) Molecular weight control agent (% by weight) n-butane 1 or less 2 or less t-butene 1 or less 2 or less 1,3-butadiene 3 or less 2 or less i-pentane 15 to 30 5 or less n-pentane 25 to 30 25 to 35 1-pentene 5 or less 2 or less 2-methyl-1-butene 5 to 10 5 to 10 t-2-pentene 2 or less 5 to 15 c-2-pentene 2 or less 5 or less 2-methyl-2-butene 3 or less 10-20 Isoprene 10-20 1 or less 2,3-dimethylbutane 3 or less 1 or less trans-1,3-pentadiene 5 to 10 1 or less 3-methylpentadiene 3 or less 5 or less cis-1,3-pentadiene 5 to 10 5 or less Cyclopentene 0.2 or less 0.1 or less n-hexane 0.2 or less 0.1 or less Cyclopentadiene 1 or less 0.1 or less Unknown component 1 or less 0.5 or less Dicyclopentadiene 0.1 or less 0 Sum 100.0 100.0

As the hydrogenation catalyst, palladium is used in one embodiment. However, the catalyst is not limited to the palladium catalyst. Examples thereof include platinum, nickel, cobalt, rhodium, ruthenium, and the like.

The content of the hydrogenation catalyst may be 0.5 to 2.0 parts by weight based on 100 parts by weight of the oil A. If the amount of the conjugated diene compound is less than 0.5 part by weight based on 100 parts by weight of the oil A, the amount of the conjugated diene compound contained in the prepared molecular weight regulator may exceed 7% by weight, 2-methyl-1-butene and 2-methyl-2-butene are contained in the molecular weight regulator prepared in an amount of less than 20% by weight, so that the molecular weight can not be controlled properly.

The partial hydrogenation reaction is carried out at 80 to 160 DEG C under a pressure of 10 to 40 kgf / cm < 2 >. If the reaction is carried out at less than 80 DEG C, the time required for partial hydrogenation is more than several tens of hours, If the temperature is higher than 160 ° C, isoprene is completely hydrogenated to be converted to isopentane, and the yield of 2-methyl-2-butene is lowered.

As described above, the molecular weight regulator according to the present invention can be produced by reacting isoprene contained in the oil A with a methyl butene compound such as 2-methyl-1-butene, 2-methyl- And isopentane, it is economical compared to simply removing the isoprene content, which is a component for increasing the average molecular weight and the molecular weight distribution of the petroleum resin, by effectively inducing gel formation in the petroleum resin production.

When the amount of the conjugated diene compound is more than 7% by weight based on the total weight of the molecular weight modifier, the above-mentioned molecular weight modifier may cause problems such as gel formation during resin production. Therefore, the content of the conjugated diene compound is preferably 7% By weight, and more preferably 2 to 5% by weight.

In addition, the molecular weight modifier prepared by the above-mentioned production method is characterized in that the content of 2-methyl-1-butene and 2-methyl-2-butene is 20% by weight or more based on the total weight of the molecular weight modifier, When the content of 2-methyl-1-butene and 2-methyl-2-butene is less than 20% by weight based on the total weight of the molecular weight regulator, the molecular weight can not be controlled or the softening point of the resin may be lowered And when the content of isoprene is more than 1 wt% based on the total weight of the molecular weight regulator, problems may arise in the economic productivity of 2-methyl-1-butene and 2-methyl-2-butene.

The molecular weight regulator according to the present invention can reduce the molecular distribution because the density of the chain structure is increased in the resin as compared with the case of controlling the molecular weight depending on the cyclic olefin-based monomers having one double bond which was the conventional production method. And it is possible to improve the color of the resin by increasing the efficiency of water separation in the acid catalyst neutralization process.

When the above-mentioned oil A is directly used in the production of a petroleum resin, since there are many chain-like conjugated diene compounds such as isoprene and the like, not only the production of gel during the production process is caused but also the molecular weight and molecular weight distribution of the obtained petroleum resin are large, . When a molecular weight regulator is used by separating and partially hydrogenolating only the isoprene component in the mixed oil from which the cyclic conjugated diene is removed, it is possible to produce a high-quality petroleum resin, but the process becomes complicated and lowers productivity and economy.

Therefore, when a petroleum resin is produced by adding an oil fraction, i.e., a molecular weight regulator, which is partially hydrogenated directly to the oil A without removing the cyclic conjugated diene, the gel formation is prevented and a desired softening point is achieved The molecular weight of the resin can be controlled favorably so that the molecular weight distribution can be narrowed and a petroleum resin improved in hue and specific gravity can be produced.

In the petroleum resin according to the present invention, the mixed oil component to be polymerized with the molecular weight regulator may also be obtained by dimerizing the cyclic conjugated diene compound contained therein, and then distilling the oil containing the cyclized conjugated diene compound to be dimerized The cyclic conjugated diene compound may be removed and used.

That is, the petroleum resin according to the present invention firstly obtains the oil A by removing the cyclic conjugated diene compound from the initial raw material (boiling range 20 to 60 ° C and oil containing unsaturated hydrocarbon having 4 to 6 carbon atoms). The oil A thus prepared is subjected to polymerization reaction in the presence of a catalyst by adding the molecular weight modifier of the present invention.

The content of the molecular weight regulator is 20 to 40 parts by weight based on 100 parts by weight of the starting raw material (boiling range 20 to 60 캜 and unsaturated hydrocarbon containing 4 to 6 carbon atoms) or oil A, 20 parts by weight , The effect is insignificant. When it is added in an amount exceeding 40 parts by weight, the resin softening point may be lowered due to an excessive molecular weight regulator.

On the other hand, in the production of petroleum resin, the present invention may further comprise addition of a polymerization regulator, a solvent, etc., and preferably a polymerization regulator such as cyclopentene, methylcyclopentene, dihydro dicyclopentadiene or dihydrodi A cyclopentadiene derivative and the like can be used as the cyclic olefin monomer.

In the present invention, the reaction substrate itself is preferably used as a solvent, but other solvents may be used. The solvent is not particularly limited as long as it does not inhibit the reaction. Examples of the solvent include 1-methoxy-2-propanol, 2-methoxyethanol, Xylene, toluene, and the like can be used.

The reaction may be carried out at 20 to 100 ° C for 1 to 8 hours. If the reaction is carried out at less than 20 ° C, a large amount Gel can be produced, and when it exceeds 100 DEG C, the resin color is deteriorated and it is not preferable. Further, when the reaction is carried out at a time less than the time required for the polymerization, the yield may be lowered, and if it exceeds, the color quality may be deteriorated.

In addition, the catalyst used in the polymerization reaction can be used without particular limitation as long as it is a Friedel-Craft catalyst generally used in a petroleum resin polymerization reaction. If the content of the catalyst is 0.003 to 0.03 part by weight based on 100 parts by weight of the oil A and less than 0.003 part by weight with respect to 100 parts by weight of the oil A, the yield may be lowered, The color quality of the resin may be deteriorated and the manufacturing cost may be increased.

As described above, the polymerization solution obtained by the polymerization reaction can neutralize the catalyst component contained in the polymerization solution, wash it, and then remove the solvent and unreacted raw materials through a degassing process to produce a petroleum resin. At this time, the neutralization and deaeration methods can be used without particular limitation, as long as they are conventional methods used for producing petroleum resins.

As described above, the petroleum resin produced by the polymerization reaction has a weight average molecular weight of 1,000 to 3,500 g / mol and a molecular weight distribution of 2.8 or less. The molecular weight and the degree of distribution of the petroleum resin are controlled by the addition of a molecular weight modifier. When the weight average molecular weight and the molecular weight distribution exceed the above range, the flowability may be lowered.

If the specific gravity of the petroleum resin exceeds 0.96, the wetting area of the filler per resin unit mass may be lowered when the resin is used for traffic paint, and the flowability may be lowered.

The petroleum resin preferably has a softening point of 93 to 97 캜 and an acid value of 2.5 to 2.9. If the softening point is lower than 93 ° C, the fluidity may rise but may cause blocking of the product. If the softening point exceeds 97 ° C, the fluidity may be lowered. If the acid value is less than 2.5, the fluidity may decrease, There is a possibility that the settling degree is deteriorated. (The degree of precipitation shows the degree of precipitation of the glass beads in the HMRM composition, which shows a tendency to deteriorate as the value increases)

The composition for traffic paint of the present invention comprises a petroleum resin, glass beads, synthetic wax, plasticizer and inorganic pigment, wherein the composition comprises 10 to 20% by weight of petroleum resin, 50 to 65% by weight of calcium carbonate, 15 to 20%, synthetic wax 0.01 to 1% by weight, plasticizer 0.5 to 2% by weight, and inorganic pigment 2 to 6% by weight.

If the amount of the petroleum resin is less than 10% by weight, the road adhesion may be deteriorated and filler binding may not be performed properly. If the amount of the petroleum resin is more than 20% by weight, the fluidity may be increased but the cost of the composition may be increased.

The calcium carbonate serves to increase the compressive strength of the traffic paint. If it is less than 50% by weight, the compressive strength may be lowered. If it exceeds 65% by weight, the cost of the composition may be increased.

The glass beads serve as an additive for reflecting the light reflected by the head light of an automobile in the traffic paint, thereby enhancing visibility at night. If less than 15% by weight, visibility at night may be deteriorated, and if it exceeds 20% by weight, And precipitation can be deteriorated.

The synthetic wax serves to improve flow and spreadability in traffic paints, preferably polyethylene wax. The synthetic wax may be present in an amount of 0.01 to 1% by weight. When the amount of the synthetic wax is less than 1% by weight, the flowability and spreadability (indicating a degree of flat spreading of the traffic paint composition on the road, , And if it exceeds 1% by weight, the compressive strength may be lowered.

The plasticizer serves to improve the flowability in the traffic paint, and uses process oil. If the plasticizer is less than 0.5% by weight, the flowability may be lowered. If the plasticizer is more than 2% by weight, the whiteness, compressive strength and sedimentation may be lowered.

The inorganic pigment serves to improve whiteness in traffic paint, and it is preferable to use titanium dioxide. If it is less than 2% by weight, the whiteness may be lowered, and if it is more than 6% by weight, the flowability may be deteriorated.

The composition for a traffic paint of the present invention may have a fluidity of less than 55 seconds as measured using a Zahn Cup having an outlet diameter of 7 mm at 220 ° C.

In addition, the wear resistance calculated by the following formula 1 may be 20 mg / 100 cycles or less.

<Formula 1>

Wear resistance = (A-B) / 2

In this equation, A is the weight of the specimen before 200 cycles of abrasion using SEISAKU-SHO LTD. Acid rotary abrasion tester, and B is the weight of the specimen worn 200 times using SEISAKU-SHO LTD. Acid rotary abrasion tester.

As a result, it is possible to uniformly apply the whole portion of the road surface to be applied on the road surface at an appropriate speed, thereby providing a composition for traffic paint having excellent workability and good strength.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[ Example ]

Manufacturing example  1. Preparation of molecular weight regulator

25 g of a palladium catalyst was placed in a 5-liter stainless steel pressure reactor, and the catalyst was activated for 5 hours while passing hydrogen at 150 캜. The dipentaizer top fraction was heated at 140 ° C for 6 hours, and the resulting dimer and dimer components were removed as high boiling point compounds by distillation. 4 L of the oil fraction from which the high-boiling point compound was removed (hereinafter referred to as oil A) was introduced into the reactor and hydrogenation was carried out for about 3 hours at a total pressure of 25 kgf / cm 2 and a reaction temperature of 120 ° C., A modifier was prepared.

Manufacturing example  2. Petroleum resin -1 manufacture

39 parts by weight of the molecular weight modifier prepared in Preparation Example 1 and 23 parts by weight of dihydrodicyclopentadiene as a polymerization modifier were mixed with 100 parts by weight of the oil A and used as a polymerization raw material for producing petroleum resin. The composition of the oil A and the molecular weight modifier used in the polymerization reaction are shown in Table 1 above. The catalyst solution was used as 0.03 parts by weight of solid AlCl ₃ powder dispersed in xylene. 500 ml of xylene was placed in a 2.4-liter stainless steel pressure reactor, and the temperature was maintained at 45 ° C under a pressure of 1.6 kgf / cm ^2. Then, 0.3 ml of the catalyst solution and 200 ml of the raw material were injected simultaneously, This was about 2 hours. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was taken out, neutralized with the same amount of water as that of the polymerization solution, and washed with water. The oil layer was separated and then the oil layer was stripped at 5 mmHg for 10 minutes Followed by stripping to remove the remaining low boiling point components to prepare a solid petroleum resin.

Manufacturing example  3. Petroleum resin -2 manufacture

38 parts by weight of the molecular weight modifier prepared in Preparation Example 1 and 21 parts by weight of dihydrodicyclopentadiene as a polymerization modifier were mixed with 100 parts by weight of the oil A to prepare a polymerization raw material for producing petroleum resin. The composition of the oil A and the molecular weight modifier used in the polymerization reaction are shown in Table 1 above. The catalyst solution was used as 0.03 parts by weight of solid AlCl ₃ powder dispersed in xylene. 500 ml of xylene was placed in a 2.4-liter stainless steel pressure reactor, and the temperature was maintained at 45 ° C under a pressure of 1.6 kgf / cm ^2. Then, 0.3 ml of the catalyst solution and 200 ml of the raw material were injected simultaneously, This was about 2 hours. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was taken out, neutralized with the same amount of water as that of the polymerization solution, and washed with water. The oil layer was separated and then the oil layer was stripped at 5 mmHg for 10 minutes Followed by stripping to remove the remaining low boiling point components to prepare a solid petroleum resin.

Manufacturing example  4. Petroleum resin -3 manufacture

To 100 parts by weight of the oil A, 33 parts by weight of the molecular weight modifier prepared in Preparation Example 1 were mixed and used as a polymerization raw material for producing a petroleum resin. The composition of the oil A and the molecular weight modifier used in the polymerization reaction are shown in Table 1 above. The catalyst solution was used as 0.03 parts by weight of solid AlCl ₃ powder dispersed in xylene. 500 ml of xylene was placed in a 2.4-liter stainless steel pressure reactor, and the temperature was maintained at 45 ° C under a pressure of 1.6 kgf / cm ^2. Then, 0.3 ml of the catalyst solution and 200 ml of the raw material were injected simultaneously, This was about 2 hours. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was taken out, neutralized with the same amount of water as that of the polymerization solution, and washed with water. The oil layer was separated and then the oil layer was stripped at 5 mmHg for 10 minutes Followed by stripping to remove the remaining low boiling point components to prepare a solid petroleum resin.

Comparative Manufacturing Example  One

105 parts by weight of dihydrodicyclopentadiene as a polymerization regulator was mixed with 100 parts by weight of the oil A to prepare a polymerization raw material for producing a petroleum resin. The composition of the oil A and the molecular weight modifier used in the polymerization reaction are shown in Table 1 above. The catalyst solution was used as 0.03 parts by weight of solid AlCl ₃ powder dispersed in xylene. 500 ml of xylene was placed in a 2.4-liter stainless steel pressure reactor, and the temperature was maintained at 65 ° C under a pressure of 1.6 kgf / cm ^2. Then, 0.3 ml of the catalyst solution and 200 ml of the raw material were injected simultaneously, This was about 2 hours. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was taken out, neutralized with the same amount of water as the polymerization solution, and then washed with water. After oil separation, the oil layer was stripped at 5 mmHg for 10 minutes and stripped to remove the remaining low boiling point components to produce a solid petroleum resin.

Comparative Manufacturing Example  2

65 parts by weight of dihydrodicyclopentadiene as a polymerization regulator was mixed with 100 parts by weight of the oil A to prepare a polymerization raw material for preparing a petroleum resin. The composition of the oil A and the molecular weight modifier used in the polymerization reaction are shown in Table 1 above. The catalyst solution was used as 0.03 parts by weight of solid AlCl ₃ powder dispersed in xylene. 500 ml of xylene was placed in a 2.4-liter stainless steel pressure reactor, and the temperature was maintained at 65 ° C under a pressure of 1.6 kgf / cm ^2. Then, 0.3 ml of the catalyst solution and 200 ml of the raw material were injected simultaneously, This was about 2 hours. The reaction temperature was maintained within ± 1 ° C using a heat exchanger. After about 6 hours from the start of the continuous reaction, the polymerization solution in the reactor was taken out, neutralized with the same amount of water as that of the polymerization solution, and washed with water. The oil layer was separated and then the oil layer was stripped at 5 mmHg for 10 minutes Followed by stripping to remove the remaining low boiling point components to prepare a solid petroleum resin.

The physical properties of the petroleum resins prepared in the above Production Examples and Comparative Production Examples were measured as follows, and the results are shown in Table 2 below.

(1) Measurement of softening point

The softening point was measured by raising the temperature by 5 ° C / minute using an automatic softening point measuring machine (model: ASPT-S2-01, manufactured by Oh Sung Machinery Co., Ltd.).

(2) Color measurement

The color was measured in Gardner units in a 10 mm quartz cell by dissolving the resin in toluene at 50 wt% using an automatic colorimeter (product name: Tintometer PFX-195, manufactured by Robibond).

(3) Density measurement

Specific gravity was measured using an automatic solid specific gravity meter (product of Alpha Miller, model name SD-200L).

(4) Acid value measurement

5 g of petroleum resin was completely dissolved in 20 ml of toluene, and then 5 ml of Ethyl Alchohol and 5 ~ 6 drops of phenolphthalein indicator were added and the solution was titrated with 0.1 N alcoholic KOH solution using Micro Burrete while stirring. And the time when the fine red color was maintained for more than 10 seconds as an end point was calculated by the following formula 2.

<Formula 2>

Acid Value = V (ml) x 56.11 x 0.1 / Sample Weight (g)

Where V is the appropriate amount of 0.1 N alcoholic KOH.

(5) Measurement of molecular weight and molecular weight distribution

The polystyrene reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (product of Hewlett Packard Co., model name HP-1100). The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of 4000 ppm and 100 μl was injected into GPC. The mobile phase of GPC was run at a flow rate of 1.0 mL / min using tetrahydrofuran and the assay was performed at 30 &lt; 0 &gt; C. The column was connected in series with three Agilent Plgel (1,000 + 500 + 100A). The detector was measured at 30 DEG C using an RI detector (HP-1047A, manufactured by Hewlett-Packard). At this time, PDI (molecular weight distribution) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

division Petroleum Resin -1 Petroleum resin-2 Petroleum resin-3 Comparative Preparation Example 1 Comparative Preparation Example 2 Softening point () 94.5 95.5 94 100 95 color 5 5 6- 9- 6 importance 0.957 0.959 0.952 0.99 0.98 Acid value 2.84 2.58 2.87 2.5 2.1 Weight average molecular weight (Mw) 2849 2413 3417 2126 2616 Molecular weight distribution (Mw / Mn) 2.53 2.32 2.75 1.89 2.3

As described above, the petroleum resin produced by the process of the present invention has a weight average molecular weight of 1000 to 3500 g / mol, a molecular weight distribution of 2.8 or less, and a specific gravity of 0.97 or less, thereby improving the wetting area of the filler per unit mass, , The fluidity can be improved when the softening point is applied to the product at 95 ° C or less, and it is confirmed that the effect of increasing the miscibility with the filler can be obtained by imparting a polar group to the nonpolar petroleum resin having an acid value of 2.5 or more.

< Example  1 to 3, Comparative Example  1>

The petroleum resin obtained in Production Examples 2 to 4 and the additives were compounded in the composition shown in Table 3 to prepare a composition for traffic paint.

Component (% by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Petroleum Resin -1 14 - - - Petroleum resin-2 - 14 - - Petroleum resin-3 - - 14 Petroleum resin-4 - - - 14 Petroleum Resin -5 14 Petroleum Resin -6 14 Polyethylene wax One One One One One One Process oil 2 2 2 2 2 2 Titanium oxide 4 4 4 4 4 4 Glass bead 16 16 16 16 16 16 Calcium carbonate 63 63 63 63 63 63 total 100 100 100 100 100 100

Petroleum resin-1: Petroleum resin obtained in Production Example 2, SP 94.5 DEG C, specific gravity 0.957, acid value 2.84

Petroleum resin-2: Petroleum resin obtained in Production Example 3, SP 95.5 DEG C, specific gravity 0.959, acid value 2.58

* Petroleum resin-3: Petroleum resin obtained in Production Example 4, SP 94.0 占 폚, specific gravity 0.952, acid value 2.87

* Petroleum resin-4: Our product R-1095, SP 97.5 ℃, specific gravity 0.972, acid value 2.87

Petroleum resin-5: Petroleum resin obtained in Comparative Production Example 1, SP 100 占 폚, specific gravity 0.99, acid value 2.5

* Petroleum resin-6: Petroleum resin obtained in Comparative Production Example 2, SP 95 ° C, specific gravity 0.98, acid value 2.1

* Polyethylene wax: Korea Petroleum, HS-12P, melting point: 100 ~ 110 ℃

* Process oil: Samchully Chemical Co., Dioctylphthalate

* Titanium oxide: Samchully Chemical Co., Antase form

* Glass beads: Binex, JT-1

* Calcium carbonate: Rexm, S-1000 (325mesh)

The physical properties of the composition for a traffic paint prepared in the above Examples and Comparative Examples were evaluated as follows.

1. Softening point

And measured according to ASTM E 28.

2. Flow

And measured at 220 캜 using a Zahn Cup having an outlet diameter of 7 mm. Since there is a variation in flow rate, it was always measured with the comparison object.

3. Compressive strength

The composition for traffic paint was poured into SUS Mold and then cooled at room temperature to prepare a 2 cm x 2 cm x 2 cm specimen. DAEKYUNG TECH. The strength was measured by compressing the specimen with DTU-900MH50kN until cracked.

4. Wear resistance

The composition for traffic paint was poured into SUS mold and cured at room temperature to prepare specimens. The specimens were prepared by spinning the specimens 500 times with SEISAKU-SHO LTD. Acid rotary abrasion tester, 3.

<Formula 3>

Wear resistance = (A-B) / 2

Where A is the weight of the specimen before 200 cycles of abrasion and B is the weight of the specimen of 200 cycles of abrasion.

division Softening point
() Flow rate
(sec) Compressive strength
(Kgf / cm2) Wear resistance (mg / 100cycle) Example 1 124.5 55 273 19.7 Example 2 125.2 48 272 19.5 Example 3 125.6 47 275 20.1 Comparative Example 1 122.5 75 231 19.9 Comparative Example 2 123.7 67 225 12 Comparative Example 3 124.3 64 243 11

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (11)

Petroleum resin, calcium carbonate, glass beads, synthetic waxes, plasticizers, and inorganic pigments. The method according to claim 1,
Wherein the petroleum resin has a weight average molecular weight of 1,000 to 3,500 g / mol. The method according to claim 1,
Wherein the molecular weight distribution of the petroleum resin is 2.8 or less. The method according to claim 1,
Wherein the petroleum resin has a softening point of 93 to 97 占 폚. The method according to claim 1,
Wherein the petroleum resin has a specific gravity of 0.96 or less. The method according to claim 1,
Wherein the petroleum resin has an acid value of 2.5 to 2.9. The method according to claim 1,
The composition comprises 10 to 20% by weight of petroleum resin, 50 to 65% by weight of calcium carbonate, 15 to 20% of glass beads, 0.01 to 1% by weight of synthetic wax, 0.5 to 2% by weight of plasticizer and 2 to 6% %, Based on the total weight of the composition. 8. The method of claim 7,
Wherein the petroleum resin is prepared by reacting oil A and a molecular weight modifier. 9. The method of claim 8,
Wherein the molecular weight modifier is added in an amount of 20 to 40 parts by weight based on 100 parts by weight of the oil A. 9. The method of claim 8,
Wherein the oil A is prepared by heating the oil containing unsaturated hydrocarbons having 4 to 6 carbon atoms to remove the dimer and the dimer component. 9. The method of claim 8,
Wherein the molecular weight regulator is prepared by heating a fraction containing unsaturated hydrocarbons having 4 to 6 carbon atoms to remove dimer and dimer components and then adding a hydrogenation catalyst to partially hydrogenate the composition.