JP4802124B2 - Primer composition for melting type road marking paint - Google Patents

Description

  The present invention relates to a primer composition for a melt-type road marking paint.

  Conventionally, when a melt-type road marking paint is applied to a concrete road surface, an asphalt road surface, etc., it is known to form a primer layer between the two in order to improve the adhesion between the road surface and the road marking paint. When the road marking paint is applied directly on the road surface without using the primer composition, there is a problem that the applied coating is peeled off from the road surface.

  It is also known to use a primer composition to improve the adhesion between an old asphalt surface or coating film surface and a newly applied coating film. By applying a primer composition to an old asphalt surface or paint film surface, the surface is dissolved, and the surface is refreshed by melting with the resin forming the road surface or paint film surface. It is known that tackiness can be imparted to the coating film surface.

  In such a primer composition, an alkyd resin, vinyl chloride-vinyl acetate copolymer resin, hydrocarbon resin (petroleum resin), natural rubber, synthetic rubber, or the like is used as a resin component. And is used as a resin concentration of about 20%. However, with the conventional primer composition as described above, sufficient adhesive force cannot be obtained between the road surface and the road marking paint, strong shearing force due to large vehicles, impact due to tire chains, etc., road surface and paint film surface in winter and summer There is a problem that the road marking paint is easily peeled off due to the stress due to the difference in thermal expansion coefficient.

  As a primer composition for solving such a problem, a primer composition comprising a terpene resin having a softening point of 30 ° C. or less, an aliphatic petroleum resin having a softening point of 60 to 100 ° C., and rubber has been disclosed (for example, patent documents). 1). It is described that the road marking paint can be strongly adhered to the road surface and can prevent the road marking paint from peeling for a long period of time by having such a composition. However, toluene is added to the primer composition as a solvent, and there is a danger of fire because there is a fire such as propane gas direct fire when installing road marking paint. The impact is also great. Moreover, since it is desired to reduce VOC (volatile organic compounds) due to recent stricter environmental regulations, a primer composition that does not contain toluene or the like used in conventional primer compositions is desired. Yes.

Japanese Examined Patent Publication No. 7-68465

  The present invention solves such a conventional problem, and an object of the present invention is to provide a primer composition having a sufficient adhesive force without using a VOC such as toluene.

That is, the present invention provides the following primer composition for melt type road marking paint.
(1) Based on 100 parts by weight of the total composition,
(A) 20-30 parts by weight of aliphatic petroleum resin (B) 5-10 parts by weight of synthetic rubber, and (C) 25-35 parts by weight of a high-boiling aromatic solvent having a boiling point of 150-260 ° C. Primer composition for marking paint.
(2) Furthermore,
(D) Primer composition for melt type road marking paint according to (1), comprising 1 to 10 parts by weight of surfactant and (E) 30 to 40 parts by weight of water.
(3) The primer composition for a melt-type road marking paint according to (1) or (2), wherein the boiling point of the high-boiling aromatic solvent (C) is 160 to 210 ° C.
(4) The melt type road marking according to any one of (1) to (3), wherein the amount of the high boiling point solvent (C) is 100 to 150 parts by weight with respect to 100 parts by weight of the aliphatic petroleum resin. Primer composition for paint.

  The present invention can reduce the amount of solvent volatilization by using a high-boiling aromatic solvent, that is, a primer composition having a small impact on the environment, a low risk of fire, and sufficient adhesive strength. Can be provided.

The present invention is based on 100 parts by weight of the total composition
(A) 20-30 parts by weight of aliphatic petroleum resin (B) 5-10 parts by weight of synthetic rubber, and (C) 25-35 parts by weight of a high-boiling aromatic solvent having a boiling point of 150-260 ° C. The present invention relates to a primer composition for a marking paint.

  As the aliphatic petroleum resin (A) in the present invention, a fraction containing an unsaturated hydrocarbon having 5 carbon atoms in naphtha as a main component (hereinafter also referred to as “C5 fraction”), an unsaturated carbonization having 9 carbon atoms. Examples thereof include a fraction containing hydrogen as a main component (hereinafter also referred to as “C9 fraction”), or a polymer obtained by cationic polymerization using a mixture thereof as a monomer.

  Examples of the compound constituting the C5 fraction include 1,3-pentadiene, isoprene, butadiene, 2-methyl-2-butene and the like.

  Examples of the compound constituting the C9 fraction include vinyl toluene, styrene, indene and methyl indene.

  In addition, an acid-modified aliphatic petroleum resin can also be suitably used. As a method for producing an acid-modified aliphatic petroleum resin, for example, there is a method in which an unsaturated carboxylic acid or an acid anhydride thereof is reacted with the aliphatic petroleum resin under heating. Examples of unsaturated carboxylic acids or acid anhydrides thereof include maleic acid, citraconic acid, itaconic acid, maleic anhydride, cytosolanic anhydride, itaconic anhydride, and other acids such as lauric acid, myristic acid, palmitic acid, And oleic acid.

  Among these, as the aliphatic petroleum resin (A) used in the present invention, 1,3-pentadiene is preferable because it is desirable to select a petroleum resin of the same system in consideration of adhesiveness with a melt-type road marking paint. An aliphatic petroleum resin which is obtained from one or more of isoprene, 2-methyl-2-butene, cyclopentadiene and the like and is not acid-modified is preferable.

  As the aliphatic petroleum resin (A) used in the present invention, the aliphatic petroleum resin and acid-modified aliphatic hydrocarbon may be used alone or in combination with other resins. Examples of other resins include modified hydrocarbon resins other than those described above, hydrocarbon resins, raw rosin, maleated raw rosin, and the like. These can be mixed at an arbitrary ratio, but the total amount of these resins in the total amount of the aliphatic petroleum resin (A) is preferably 5 to 25% by weight, more preferably 10 to 20% by weight. If it is less than 5% by weight, it tends to be inferior in adhesion to the melt-type road marking paint, and if it exceeds 25% by weight, the fluidity of the primer tends to be poor.

  The blending amount of the aliphatic petroleum resin (A) is preferably 20 to 30 parts by weight based on 100 parts by weight of the total amount of the primer composition for melt type road marking paint. When the blending amount of the aliphatic petroleum resin (A) is less than the above range, the adhesiveness with the melt type road marking paint tends to be inferior, and when it exceeds the above range, the flowability of the primer tends to be poor.

  In the present invention, the synthetic rubber (B) is used together with the aliphatic petroleum resin (A). The synthetic rubber (B) is not particularly limited, and examples thereof include polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, styrene rubber, and hydrogenated styrene-butadiene rubber. Among these, styrene-butadiene rubber is preferable from the viewpoint of modifying asphalt.

  The blending amount of the synthetic rubber (B) is preferably 5 to 10 parts by weight based on 100 parts by weight of the total amount of the primer composition for melt-type road marking paint. When the blending amount of the rubber (B) is less than the above range, the asphalt is not sufficiently modified and the adhesion property of the melt-type road marking paint is inferior, and when it exceeds the above range, the flowability of the primer tends to deteriorate. In this respect, the compounding amount of the synthetic rubber (B) is more preferably 10 to 50 parts by weight and further preferably 20 to 30 parts by weight with respect to 100 parts by weight of the aliphatic petroleum resin (A). .

  As the high boiling point aromatic solvent (C) used in the present invention, those having both the solubility of the aliphatic petroleum resin (A) and the synthetic rubber (B), the solubility of asphalt as the road surface, the flash point, and the emulsion stability. preferable.

  The boiling point of the high-boiling aromatic solvent (C) used in the present invention is 150 to 260 ° C, more preferably 160 to 210 ° C, and particularly preferably 180 to 210 ° C. When the boiling point is less than 150 ° C., the primer tends not to be a uniform coating film, and when it exceeds 260 ° C., the asphalt dissolving power tends to be inferior.

  The blending amount of the high-boiling aromatic solvent (C) is preferably 25 to 35 parts by weight based on 100 parts by weight of the total amount of the primer composition for melting road marking paint. If the blending amount of the high-boiling aromatic solvent (C) is less than the above range, the aliphatic petroleum resin (A) and the synthetic rubber (B) tend not to be dissolved. If the blending amount exceeds the above range, the emulsion stability is poor. Tend to be. From this point, the blending amount of the high boiling point aromatic solvent (C) is more preferably 50 to 300 parts by weight, and 100 to 200 parts by weight with respect to 100 parts by weight of the aliphatic petroleum resin (A). Is more preferable, and it is especially preferable that it is 100-150 weight part.

  Examples of the high boiling point aromatic solvent (C) include aromatic compounds having 9 to 10 carbon atoms such as trimethylbenzene, tetramethylbenzene, diethylbenzene and naphthalene, or mixtures thereof. Among these, diethylbenzene and a mixture thereof are preferable from the viewpoint of good dissolving power of asphalt, aliphatic petroleum resin (A), and synthetic rubber (B). Specifically, SWAZOL 1500 (manufactured by Maruzen Petrochemical Co., Ltd., boiling point 180.5-208.5 ° C., flash point 64 ° C., combustion point 71 ° C.) Cactus Solvent P-150, Japan Energy Co., Ltd., boiling point 180- 210 ° C., flash point 64 ° C., combustion point 71 ° C.) and the like.

  In addition to the high boiling point aromatic solvent (C), a solvent other than the high boiling point aromatic solvent (C) can also be used. Examples of the solvent other than the high-boiling aromatic solvent (C) include ketone solvents such as methyl isobutyl ketone, diisobutyl ketone and cyclohexanone, and alcohol solvents such as n-butanol and isopropyl alcohol.

  Furthermore, it is preferable that the primer composition of the present invention further contains a surfactant (D) and water (E). A high boiling point aromatic solvent (C) in which an aliphatic petroleum resin (A) or the like is dissolved is emulsified in water (E) using a surfactant (D) to form an emulsified liquid. The amount of solvent (C) used can be reduced.

  Examples of the surfactant (D) include lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, glycerin fatty acid ester and the like.

  The blending amount of the surfactant (D) is preferably 1 to 10 parts by weight based on 100 parts by weight of the total primer composition for melt-type road surface display paint. When the surfactant (D) is less than the above range, there is a tendency that it cannot be sufficiently emulsified, and when it exceeds the above range, the adhesion of the melt-type road marking paint to asphalt tends to be inhibited. From this point, the blending amount of the surfactant (D) is preferably 10 to 100 parts by weight, and preferably 10 to 50 parts by weight with respect to 100 parts by weight of the aliphatic petroleum resin (A).

  Moreover, the blending amount of water (E) is preferably 30 to 40 parts by weight based on 100 parts by weight of the total amount of the primer composition for melt-type road surface display paint. Furthermore, it is preferable to contain 100-200 weight part with respect to 100 weight part of aliphatic petroleum resin (A), and it is preferable that it is 100-150 weight part.

  In consideration of environmental impact, the primer composition is preferably classified as a non-hazardous material. The non-hazardous material referred to here is a flammable liquid amount of 40% or less, a flash point of 40 ° C. or more, and a combustion point of 60 ° C. according to the fourth class flammable liquid judgment standard stipulated in the Fire Service Law. If it is the above, it is classified as non-dangerous goods. Therefore, in the present invention, the amount of flammable liquid is preferably 5 to 40% by weight, and more preferably 25 to 35% by weight. If the amount of the flammable liquid is less than 5% by weight, the aliphatic petroleum resin (A) and the rubber (B) tend not to be dissolved.

  The flash point is preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. The higher the flash point, the better. The upper limit is not particularly limited, but 70 ° C. or lower is preferable from the viewpoint of the drying property of the primer. A flash point of less than 40 ° C. is not preferable because the risk of fire due to direct fire work during construction of road marking paint is increased.

  The combustion point is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. Like the flash point, the higher the combustion point, the better. The upper limit is not particularly limited, but it is preferably 100 ° C. or less from the viewpoint of the drying property of the primer. A burning point of less than 60 ° C. is not preferable because the risk of fire due to direct fire work or the like during construction of the road marking paint increases.

  The method for producing the primer composition of the present invention is not particularly limited, and a normal method for producing a primer composition can be employed. For example, there may be mentioned a method in which an aliphatic petroleum resin (A) is dissolved in a high-boiling aromatic solvent (C) and the solution and water are emulsified with an emulsifier to form a liquid. A normal method can be used as the emulsification method, and examples thereof include a method using a homogenizer.

  The primer composition of this invention can improve the adhesiveness of a road surface and a road marking coating material by apply | coating on a road surface. In addition, by applying to an old asphalt surface or paint surface, it is possible to obtain a surface strength improvement effect and an adhesive recovery effect.

The primer composition of the present invention is usually applied on the road surface to a thickness of about 15 to 25 g / m ² after drying in order to achieve a desired effect as a primer. The melt type road marking coating applied on the primer composition of the present invention is not particularly limited, and any conventional one can be used. For example, a resin that contains a meltable resin, a softener, a colorant, and a filler as main components and melts at about 60 to 110 ° C. Examples of the meltable resin include C5 aliphatic hydrocarbon resins and C9 aliphatic hydrocarbon resins. Examples of the softening agent include polyethylene wax and plasticizer. Examples of the colorant include titanium oxide and zinc oxide. Examples of the filler include calcium carbonate, glass beads, cryolite, barium sulfate, hydrous magnesium silicate and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not limited to these Examples. Unless otherwise specified, “parts” represents parts by weight and “%” represents% by weight.

Example 1
In a 1 L poly beaker, 250 parts by weight of an aliphatic petroleum resin and 50 parts by weight of styrene-butadiene rubber were added to 300 parts by weight of Swazol 1500 (manufactured by Maruzen Petrochemical Co., Ltd.), and dissolved by stirring. Other components were blended and emulsified using a homogenizer to obtain a primer composition.

Component Weight Part Swazol 1500 300
Aliphatic petroleum resin 250
Styrene-butadiene rubber 50
Surfactant (polyoxyethylene alkyl ether and lauryl sulfate sodium salt) 60
Water 340
Antifoam 2

Comparative Example 1
The following composition primer composition was prepared.

Component weight part Toluene 80
Aliphatic petroleum resin 125
Styrene-butadiene rubber 25
Alcohol 30

Test Example 1 (Comparison of drying properties)
After applying the primer composition, a melt type road marking paint is applied thereon as a top coat. Therefore, if the primer composition is not sufficiently dried, blisters or pinholes are generated in the melt type road marking paint film. The time until no pinhole was generated in the coating film of the melt type road marking paint (meaning the drying time of the primer composition) was measured. In order to make the dry coating amount of the primer composition the same, the wet coating amount of the primer composition of Example 1 was made half the wet coating amount of the primer composition of Comparative Example 1.

  After applying the primer composition to an aluminum plate of 75 x 150 x 1 mm, melt the road marking paint with the following composition at 200 ° C every 5 minutes, and use a special applicator to give a coating width of 60 mm and a film thickness of 1.5 mm It was applied to. At that time, the case where a pinhole was generated was evaluated as x, and the case where a pinhole was not generated and a uniform coating film was evaluated as ◯.

<Melting type road marking paint>
Component Weight Part Thermoplastic petroleum resin 160
Titanium oxide 45
Calcium carbonate 300
Sasuiishi 300
Glass beads 160
Polyethylene wax 15
Plasticizer 20

  The results are shown in Table 1.

Test Example 2 (Adhesion of melt-type road marking paint using impact tester)
Adhesion between the primer composition and the melt-type road surface marking paint was examined using a Charpy tester.

  FIG. 1A is a perspective view of the test piece used, and FIG. FIG. 2 is an explanatory diagram of the Charpy tester used.

  A predetermined amount of primer 3 was applied to asphalt block 2 having a size of 60 × 70 × 25 mm, and after sufficiently drying, melt-type road marking paint 4 was applied. Further, the surface was polished, and a 10 mm square and 60 mm long iron square member 5 was fixed with an adhesive and left for 24 hours. The excess adhesive around the square member 5 and the melt-type road marking paint were scraped off and used as a test piece 1. A total of three types of test pieces were prepared: a test piece using no primer, a test piece using the primer of Example 1, and a test piece using the primer of Comparative Example 1.

  Each obtained test piece 1 was installed in the Charpy testing machine shown in FIG. In the Charpy testing machine, a frame 11 is erected on a base 10, and a hammer 12 is rotatably attached to the frame 11. The frame 11 is further provided with a scale plate 14, and the rotation angle of the hammer 12 is read by a pointer 15 attached coaxially with the rotation axis of the hammer 12. The scale plate 14 is engraved with the graduation of the perpendicular line downward from the rotation axis being 0 degrees and the graduation of the perpendicular line downward from the rotation axis being 180 degrees. The angle formed between the hammer 12 in the state of being locked to the hook 13 and the perpendicular is the lifting angle 17, and the angle formed between the hammer 12 and the perpendicular in the state where the hammer 12 is swung up in the opposite direction after colliding with the test piece 1. Is the swing angle 18.

  The test piece 1 was placed on the base 10 so that the longitudinal direction of the square member 5 was along the swinging direction of the hammer 12 and the contact surface of the hammer 12 and the end surface 6 of the square member 5 were in front of each other. Reference numeral 16 denotes a test piece support. With the hammer 12 applied to the hook 13, the pointer 15 was adjusted to the position of the scale 150 (lifting angle: 150 degrees), the hook 13 was removed, and the hammer 12 was shaken down by natural fall. The degree of adhesion was compared according to how many times the hammer 12 (pointer 15) was swung up in the opposite direction due to the impact of the hammer 12 colliding with the square 5 and the molten road marking paint being peeled off from the base material. That is, it can be determined that the smaller the swing angle 18 is, the higher the adhesion is.

The following test conditions were used.
(1) Hammer mass: 0.7kg
(2) Distance from the center of rotation of the hammer to the center of gravity: 0.232m
(3) Hammer lifting angle corresponding to the maximum capacity: 150 degrees (4) Distance from hammer rotation axis center to impact point: 0.3 m
(5) Hammer hitting speed: 3.3 m / s

  A new asphalt block, one that was exposed to the outdoors for 6 months, and the one that was applied to the asphalt block after the primer of Comparative Example 1 was applied and then the melt-type road marking paint was applied, and the one that was exposed to the outdoors for 6 months in total 3 Kinds were prepared. In each case, adhesion was confirmed with two types of primers and no primer. The results are shown in Table 2.

プライマーがない場合は、溶融型路面標示塗料の基材に対する密着性が弱く、層間剥離に近い形で基材からとれており、結果として振り上げ角が高く出る。一方、プライマーを使用すると、溶融型路面標示塗料の基材に対する密着性が強くなるために、溶融型路面標示塗料は基材と一緒に取れる（アスファルトブロック内で凝集破壊を生じる）。すなわち振り上げ角が小さくなる。さらに実施例１のプライマーと比較例１のプライマーにおいて、その振り上げ角に差がないことから、実施例１のプライマーの密着性は比較例１のプライマーと同等と判断できる。

In the absence of the primer, the adhesion of the melt-type road marking paint to the base material is weak, and it is removed from the base material in a form close to delamination, resulting in a high swing angle. On the other hand, when the primer is used, the adhesion of the melt-type road marking paint to the base material becomes strong, so that the melt-type road marking paint can be taken together with the base material (causing a cohesive failure in the asphalt block). That is, the swing angle is reduced. Furthermore, since there is no difference in the swing angle between the primer of Example 1 and the primer of Comparative Example 1, it can be judged that the adhesion of the primer of Example 1 is equivalent to the primer of Comparative Example 1.

(A) is a perspective view of the test piece used by the test example, (b) is the side view. It is explanatory drawing of the Charpy testing machine used by the test example.

Explanation of symbols

1 Test piece 2 Asphalt block 3 Primer 4 Melting type road marking paint 12 Hammer 14 Scale plate 15 Pointer 17 Lifting angle 18 Swing up angle

Claims (4)

Based on 100 parts by weight of the total composition,
(A) 20-30 parts by weight of aliphatic petroleum resin (B) 5-10 parts by weight of synthetic rubber, and (C) 25-35 parts by weight of a high-boiling aromatic solvent having a boiling point of 150-260 ° C. Primer composition for marking paint. further,
The primer composition for melt type road marking paint according to claim 1, comprising (D) 1 to 10 parts by weight of a surfactant and (E) 30 to 40 parts by weight of water. The primer composition for melting road marking paint according to claim 1 or 2, wherein the boiling point of the high-boiling aromatic solvent (C) is 160 to 210 ° C. The primer composition for a melt-type road marking paint according to any one of claims 1 to 3, wherein the amount of the high boiling point solvent (C) is 100 to 150 parts by weight with respect to 100 parts by weight of the aliphatic petroleum resin.

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