JPS6156261B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition for hot-melt traffic paint. More specifically, the present invention relates to a composition for hot-melt traffic paint that has excellent heat stability and whiteness, and has a coating film that has high stain resistance and compressive strength and suppresses the occurrence of hair cracks. BACKGROUND OF THE INVENTION Various types of traffic paints, such as air-drying types, heated spray types, and heat-melting types, are known for use in road markings and other markings. Among these traffic paints, heat-melting traffic paints are preferred when applying on roads with heavy traffic, as they cure the paint film within a short period of time, reducing installation time. . Conventionally, it has been known that maleated rosin, alkyd resin, epoxy resin, polyester, etc. can be used as a tackifying agent that is a component of a hot-melt traffic paint composition. Modified rosin products such as rosin-based rosin are said to be the best. However, since modified rosin products rely on natural products as raw materials, they cannot meet the remarkable growth in demand in recent years. Hydrocarbon resins, which can be produced industrially at low cost and easily, are attracting attention as tackifiers that can replace conventional modified rosin products. The hydrocarbon resin is produced from an aliphatic hydrocarbon resin produced from an aliphatic unsaturated hydrocarbon-containing fraction with a boiling point range of -20 to +100°C and an aromatic unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C. It is classified as aromatic hydrocarbon resin. When aromatic hydrocarbon resins or their modified products are used in hot-melt traffic paint compositions, stain resistance and Although it has outstanding advantages such as a coating film with high compressive strength and less hair crack formation, and excellent compatibility with modified rosin when used in combination with rosin, on the other hand, aromatic hydrocarbons Due to the poor hue and heat stability of the resin itself, it is not possible to obtain a heat-melting type traffic paint composition with high heat resistance stability, and in particular, it cannot be used for white traffic paint, which requires a light-colored resin, which is fatal. There are some drawbacks. Therefore, conventional aromatic hydrocarbon resins are mainly used for yellow traffic paints, and when used for white paints, they are in the form of blends with rosin-modified products, and only 50%
It was only used in the following proportions. As a result, it was difficult to say that the above characteristics achieved by using the aromatic hydrocarbon resin were sufficiently exhibited. The present invention involves the transportation of an aromatic hydrocarbon resin obtained by preheating an unsaturated hydrocarbon-containing fraction of a polymerization raw material in the presence of an α/β-unsaturated dicarboxylic acid anhydride and then polymerizing it. When used as a tackifying agent for paint, a composition for hot-melt traffic paint with excellent heat resistance stability can be obtained.
This is based on the discovery that when used as a tackifying agent for white paints in particular, a traffic paint composition with high whiteness can be obtained. Of course, the hot-melt traffic paint composition of the present invention has greater stain resistance and compressive strength than those using conventional aliphatic hydrocarbon resins or modified products thereof as tackifying agents. It has a number of characteristics such as being able to obtain a coating film that does not easily cause classics, and has excellent compatibility with modified rosin and plasticizers, and uses modified rosin such as maleated rosin as a tackifying agent. It has performance equivalent to or better than that of the hot-melt traffic paint composition. That is, the present invention provides α-
Aromatic hydrocarbon resin or its maleic anhydride obtained by polymerizing an unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C that has been preheated in the presence of β-unsaturated dicarboxylic acid anhydride. or modified product (a) with maleic acid ester and pigment
A hot-melt traffic paint composition characterized by containing (b). The hydrocarbon resin used as a tackifying agent in the hot-melt traffic paint composition of the present invention has a boiling point range that has been preheated in the presence of the α/β-unsaturated dicarboxylic acid anhydride. It is an aromatic hydrocarbon resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction at 140 to 280°C. More specifically, this aromatic hydrocarbon resin is produced by the following method. The unsaturated hydrocarbon-containing fraction used to produce this aromatic hydrocarbon resin has a boiling point range of 140 to 280, which is produced as a by-product during thermal decomposition such as steam cracking of petroleum, sand cracking, and hydroreforming. ℃, and this unsaturated hydrocarbon-containing fraction mainly contains C ₈ to C ₁₂ aromatic hydrocarbon components. This unsaturated hydrocarbon-containing fraction is heat-treated in the presence of an α/β-unsaturated dicarboxylic acid anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc. before polymerization. The amount of α/β-unsaturated dicarboxylic acid anhydride used is usually in the range of 1 to 20% by weight based on the unsaturated hydrocarbon component in the unsaturated hydrocarbon-containing fraction, and the temperature of the preheating treatment is usually 50% by weight. to 250℃. During this preheating treatment, catalytic amounts of aluminum halides, boron halides or their complexes, Lewis acids such as iron halides, tin halides, zinc halides, etc.; sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid; When coexisting with inorganic protonic acids such as; organic protonic acids such as organic carboxylic acids, organic sulfonic acids, and phenolic acids,
The aromatic hydrocarbon resin is preferable because it further improves the hue and heat resistance stability. The unsaturated hydrocarbon-containing fraction, which has been preheated in the presence of α/β-unsaturated dicarboxylic acid anhydride, is then distilled to produce α/β-unsaturated dicarboxylic acid anhydride or its reaction. After removing the product, the aromatic hydrocarbon resin for the traffic paint of the present invention is obtained by polymerization in the presence of a Friedel-Crafts type catalyst and post-treatment according to a conventional method. . Further, for the purpose of adjusting the softening point of the hydrocarbon resin, if necessary, it may be copolymerized with a small amount of an unsaturated hydrocarbon-containing fraction having a boiling point range of -20 to +100°C. The aromatic hydrocarbon resin produced by this method is a solid at room temperature, and has a number average molecular weight in the range of 500 to 1500 and a softening point (ring and ball point).
It is preferable to use an aromatic hydrocarbon resin having a temperature in the range of 70 to 130° C. and a hue (Gardner of the molten resin) of 9 or less in the hot-melt traffic paint composition of the present invention. When the aromatic hydrocarbon resin produced by the above method is used in combination with a modified rosin such as maleated rosin, the aromatic hydrocarbon resin may be used unmodified. When an aromatic hydrocarbon resin is used alone, it is usually modified by the method described below. As a method for modifying the aromatic hydrocarbon resin, the method proposed by the present applicant in Japanese Patent Publication No. 39451/1983 can be applied as is. For example, a method of oxidizing an aromatic hydrocarbon resin in a liquid state such as a solution or a molten state with a molecular acid-containing gas; A method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester under heating, usually in the presence of a radical initiator, or a method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester, or a method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester, or a method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester, or a method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester, or a method in which a polar group is introduced by reacting an organic polar compound such as a carboxylic acid ester under heat, usually in the presence of a radical initiator. Examples include a method of introducing an ester bond by reacting a modified hydrocarbon resin into which a group has been introduced with a monohydric or polyhydric alcohol. When denatured by any method,
Acid value ranges from 0.1 to 30 or saponification value 0.1
It is particularly preferable to use modified aromatic hydrocarbon resins having a molecular weight of from 60 to 60 in the hot-melt traffic paint composition of the present invention. In addition to the aromatic hydrocarbon resin or its modified product, the composition for hot-melting traffic paint of the present invention contains titanium white, zinc white, yellow lead, red iron, phthalocyanine green, and various azo organic pigments. At least one pigment such as is blended as an essential component. In addition, if necessary, tackifiers such as rosin modified products such as maleated rosin; polyethylene, polypropylene, ethylene-
Resin-like materials such as vinyl acetate copolymers; fillers such as calcium carbonate, silica sand, talc, calcium sulfate; light-reflective substances such as glass beads; anti-slip agents such as cut glass; lubricants such as synthetic wax and paraffin wax. ; Dioctyl phthalate,
Plasticizers such as dibutyl phthalate, liquid paraffin, diphenyl chloride, vegetable oil, vegetable oil-modified alkyd resin, and mineral oil; heat stabilizers; or weather stabilizers are blended. The proportion of the pigment blended as an essential component in the hot-melt traffic paint composition of the present invention is usually 2 to 200 parts by weight per 100 parts by weight of the aromatic hydrocarbon resin or modified product thereof.
The preferred range is 5 to 100 parts by weight. When other components other than the two essential components consisting of an aromatic hydrocarbon resin or its modified product and a pigment are blended as necessary in the composition for hot melt type traffic paint of the present invention, the blending ratio is as follows: In the case of chemical rosin, it is usually 10 to 1000 parts by weight per 100 parts by weight of aromatic hydrocarbon resin or its modified product.
Parts by weight range, aromatic hydrocarbon resin or its modified products in the case of fillers such as calcium carbonate
Usually in the range of 50 to 1000 parts by weight per 100 parts by weight, and in the case of light reflective substances such as glass beads, usually 30 to 200 parts by weight per 100 parts by weight of aromatic hydrocarbon resin or its modified product. range. Other resinous substances, lubricants, plasticizers, heat stabilizers, weather stabilizers, etc. are blended in appropriate amounts. The aromatic hydrocarbon resin or its modified product blended into the hot-melt traffic paint composition of the present invention has particularly excellent compatibility with modified rosin products such as maleated rosin, and can be used to form a uniform composition. Therefore, it is suitable for normal use in combination with modified rosin products. Of course, even if an aromatic hydrocarbon resin or its modified product is used alone as a tackifying agent without using a rosin modified product, the excellent properties of the hot-melt traffic paint composition of the present invention will still be maintained. does not change. The composition for hot-melt traffic paint of the present invention includes, in addition to the above-mentioned aromatic hydrocarbon resin or its modified product (a) and a pigment (b); Modified product (a), pigment
(b) and a modified rosin (c); a composition comprising an aromatic hydrocarbon resin or its modified product (a), a pigment (b), and a filler (d); an aromatic hydrocarbon resin Alternatively, a composition comprising a modified product (a) thereof, a pigment (b), a modified rosin product (c), and a filler (d) can be mentioned. The method for preparing the hot-melt traffic paint composition of the present invention is to add a pigment and, if necessary, a tackifying agent such as the aromatic hydrocarbon resin or its modified product while stirring in a molten state. Examples include a method of blending other components or a method of mixing all the components and then melting them. The hot-melt traffic paint composition of the present invention can be easily applied using a conventional hot-melt traffic paint application machine. As detailed above, the hot-melt traffic paint composition of the present invention has excellent heat resistance stability,
The coating film obtained from this traffic paint has the advantage of having high stain resistance and compressive strength, and is less prone to hair cracks. Also, pigment
When titanium white or zinc white is used as (b) to form a white traffic paint, there is an advantage that a coating film with high whiteness can be obtained. Furthermore, in the hot-melt traffic paint composition of the present invention, even when an aromatic hydrocarbon resin or a modified product thereof is used alone as a tackifier, it is equivalent to or equal to the case where a conventional modified rosin product is used. It has the advantage of being able to provide a coating film with even higher performance, and when used in combination with rosin-modified products, which are normally used, it has superior compatibility with rosin-modified products compared to aliphatic hydrocarbon resins, resulting in uniform coatings. It also has the advantage of being a composition. Next, the hot-melt traffic paint composition of the present invention will be explained in more detail with reference to Examples. Note that aromatic hydrocarbon resins and modified products thereof used in Examples or Comparative Examples are shown in Reference Examples 1 to 5. Further, the evaluation method of a hot-melt traffic paint composition using these aromatic hydrocarbon resins or modified products thereof as a tackifying agent is as follows. (1) Method for preparing a composition for heat-melting traffic paint Aromatic hydrocarbon resin or its modified product and/or maleated rosin, alkyd resin, titanium, calcium carbonate, and glass beads are heated at 200°C in a predetermined ratio. A homogeneous composition was prepared by mixing for 1 hour. (2) Softening point JIS K-5665 (3) Melt viscosity After raising the temperature of the hot-melt traffic paint composition prepared by the method of (1) to 200°C,
Melt viscosity was measured using an EMILA rotational viscometer (manufactured by EMILA, Denmark). (4) Method for measuring fluidity The temperature of the hot-melt traffic paint composition prepared in (1) was maintained at 200°C, and in order to measure the fluidity, the composition was poured into a metal ladle (31 mmφ x 24
mm), quickly poured it onto a smooth stainless steel plate from a height of 30 mm, measured the major axis (a) and minor axis (b) of the disc-shaped composition, and measured the average value [(a+
b)/2] was defined as the fluidity. (5) Method for measuring whiteness and yellowness Prepare a test piece according to JIS K5665 5 and 6, measure L, a, and b values in Color Studio, and use these values to determine whiteness W = 100-{ (100−
L) ² + a ² + b ² } was calculated. Further, the yellowness was indicated by the b value. (6) Method for measuring heat resistance stability After heating the composition prepared by method (1) at 240°C for 2 hours, test pieces were prepared according to JIS K5665 5 and 6, and the whiteness of the coating film was measured. (5) and compared with before heating. (7) Method for evaluating stain resistance Test pieces were prepared from the hot-melt traffic paint composition prepared in (1) in accordance with JIS K5665 5 and 6. After 24 hours, a powder consisting of 95 parts by weight of red clay and 5 parts by weight of carbon black was sprinkled on the paint film, the powder was removed with a brush, and the whiteness of the paint film was measured according to (5). It is expressed as the retention rate of whiteness before contamination. (8) Compressive strength JIS K5665. However, the compression speed is 50mm per minute.
And so. (9) Hair crack test method After irradiating a test piece prepared in accordance with JIS K5665 5 and 6 with a sunshine weather meter for 120 hours, the degree of hair crack occurrence in the coating film was observed and evaluated in the following four stages. evaluated. A (hardly generated) B (slightly generated) C (considerably generated) D (extremely generated) Reference example 1 Boiling point range 140 to 140 with the composition listed in Table 1
Naphtha cracking fraction at 240℃ (unsaturated hydrocarbon content
49.3% by weight) was added with 4% by weight of maleic anhydride and treated at 130°C for 4 hours with stirring. The reaction solution was then distilled to obtain distillate oil with a boiling point of 120℃/20mmHg.
A yield of 93% by weight was recovered. Next, using the treated fraction obtained in this way as a raw material, 0.5% by weight of boron trifluoride ether complex catalyst was added and polymerized at 40°C for 2 hours. After the catalyst was decomposed and removed with a caustic soda aqueous solution, it was washed with water and distilled. Unreacted oil and low polymers were distilled off to obtain an aromatic hydrocarbon resin having a hue (Gardner) of 8, a softening point (ring and ball method) of 94°C, and a number average molecular weight of 730 in a yield of 41% by weight.

[Table] Reference Example 2 2% by weight in the naphtha cracked fraction used in Reference Example 1
Maleic anhydride and 0.2% by weight of anhydrous ferric chloride were added and treated at 100°C for 2 hours, followed by distillation in the same manner as in Reference Example 1 to recover distillate oil with a yield of 94% by weight. Next, using this treated fraction as a raw material, 0.5% by weight of a boron trifluoride phenol complex catalyst was added, and polymerization and post-treatment were performed in the same manner as in Reference Example 1.
An aromatic hydrocarbon resin was obtained with a yield of 44% by weight.
Next, 0.4% by weight of maleic anhydride was added to this aromatic hydrocarbon resin, and the mixture was heated at 200°C under a nitrogen atmosphere.
After stirring for an hour, a modified aromatic hydrocarbon resin having a hue (Gardner) of 7, a softening point (ring and ball method) of 97°C, a number average molecular weight of 760, and an acid value of 3.1 was obtained. Reference example 3 3% by weight in the naphtha cracked fraction used in reference example 1
After adding citraconic anhydride and 0.1% by weight of anhydrous aluminum chloride and treating at 130°C for 2 hours, distillation was performed in the same manner as in Reference Example 1 to recover 91% by weight of distillate oil. Next, using this treated fraction as a raw material, 0.4% by weight of a boron trifluoride phenol complex catalyst was added, and polymerization and post-treatment were performed in the same manner as in Reference Example 1 to produce an aromatic hydrocarbon resin with a yield of 42% by weight. Obtained. Next, add 2% by weight to this aromatic hydrocarbon resin.
of citraconic maleic acid under nitrogen atmosphere.
After stirring at 200°C for 3 hours, unreacted maleic anhydride was distilled off. Thereafter, 2% by weight of diethylene glycol was added and stirred at 200°C for 2 hours, and unreacted diethylene glycol was distilled off. Hue (Gardner) was 8, softening point (ring and ball method) was 103°C, number average molecular weight was 810, and acid value was 4.3. A modified aromatic hydrocarbon resin having a saponification value of 20.7 was obtained. Reference Example 4 Boron trifluoride phenol was produced using a mixture of 80% by weight of the treated fraction obtained in Reference Example 2 and 20% by weight of a naphtha cracked fraction having the composition shown in Table 2 and having a boiling point range of -20 to +50°C as a raw material. Add 0.5% by weight of complex catalyst
Polymerization was carried out at 30° C. for 2 hours, and post-treatment was performed in the same manner as in Reference Example 1 to obtain an aromatic hydrocarbon resin with a yield of 42% by weight. Next, 2% by weight of maleic anhydride was added to this aromatic hydrocarbon resin and heated to 200°C under a nitrogen atmosphere.
After stirring for 3 hours at
A modified aromatic hydrocarbon resin having a temperature of 95°C, a number average molecular weight of 750, and an acid value of 9.8 was obtained.

【table】

[Table] Reference Example 5 The same procedure as in Reference Example 1 was carried out by adding 0.5% by weight of boron trifluoride phenol complex catalyst to the naphtha cracked fraction used in Reference Example 1 in the presence of maleic anhydride without heat treatment. After polymerization and post-treatment
An aromatic hydrocarbon resin was obtained with a yield of 39% by weight.
Next, 0.6% by weight of maleic anhydride was added to this aromatic hydrocarbon resin, and the mixture was heated at 200°C under a nitrogen atmosphere.
After stirring for a period of time, a modified aromatic hydrocarbon resin having a hue (Gardner) of 11, a softening point (ring and ball method) of 105°C, a number average molecular weight of 800, and an acid value of 3.0 was obtained. Reference example 6 3% by weight in the naphtha cracked fraction used in reference example 1
of itaconic anhydride and 0.1% by weight of anhydrous aluminum chloride were added and treated at 130° C. for 2 hours with stirring. The reaction solution was then distilled to a boiling point of 120℃/20mm.
The distillate up to Hg was recovered with a yield of 92% by weight.
This was polymerized and post-treated in the same manner as in Reference Example 1 to obtain an aromatic hydrocarbon resin with a yield of 40% by weight. Next, add 0.8% by weight to this aromatic hydrocarbon resin.
of maleic anhydride and stirred for 2 hours at 200°C under a nitrogen atmosphere to obtain a modified aromatic hydrocarbon resin having a hue (Gardner) of 8, a softening point (ring and ball method) of 98, a number average molecular weight of 780, and an acid value of 4.0. Obtained. Examples 1 to 5, Comparative Examples 1 to 2 The aromatic hydrocarbon resins or modified aromatic hydrocarbon resins and/or maleated rosins of Reference Examples 1 to 6 were used as the tackifying agent as shown in Table 3. A hot-melt traffic paint composition was prepared with the following blending ratios. Next, the physical properties shown in Table 2 were measured for these compositions, and the results are also shown in the same table. These results show that the hot-melt traffic paint composition of the present invention provides a coating film that is excellent in whiteness, heat-resistant stability, stain resistance, and compressive strength and is resistant to hair cracks. The whiteness of the coating film obtained from the hot-melt traffic paint composition (Comparative Example 1) using the aromatic hydrocarbon resin (Reference Example 5) that was polymerized without treating the polymerization raw material with maleic anhydride was It can be seen that hair cracks are likely to occur in the coating film obtained from the hot-melting traffic paint composition (Comparative Example 2) which uses only maleated rosin, and is inferior in heat stability and stain resistance.

【table】

Claims (1)

[Claims] 1. A boiling point range of 140 to 280°C when preheated in the presence of an α/β-unsaturated dicarboxylic acid anhydride selected from the group of maleic anhydride, itaconic anhydride, and citraconic anhydride. A hot melt characterized by containing (a) an aromatic hydrocarbon resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction of or a modified product thereof with maleic anhydride or a maleic acid ester, and a pigment (b). Composition for type traffic painting. 2. The number average molecular weight obtained by polymerizing an unsaturated hydrocarbon-containing fraction as component (a) is in the range of 500 to 1500, and the softening point (ring and ball method) is in the range of 70 to 130°C,
The composition for heat-melting traffic paint according to claim 1, characterized in that an aromatic hydrocarbon resin having a hue (Gartner) of 9 or less or its modified product with maleic anhydride or maleic acid ester is used. . 3. Any of claims 1 to 2, characterized in that a modified aromatic hydrocarbon resin having an acid value in the range of 0.1 to 30 or a saponide value in the range of 0.1 to 60 is used as component (a). A composition for hot melt type traffic paint. 4 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic ester
4. A composition for hot-melt traffic paint according to any one of claims 1 to 3, characterized in that it contains 2 to 200 parts by weight of pigment (b) per 100 parts by weight of (a). 5 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic ester
5. A composition for hot-melt traffic paint according to any one of claims 1 to 4, characterized in that it contains a modified rosin (c) in addition to (a) and the pigment (b). 6 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic acid ester
6. The composition for hot-melt traffic paint according to any one of claims 1 to 5, characterized in that it contains a filler (d) in addition to (a) and the pigment (b). 7 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic acid ester
The heat-melting type traffic paint according to any one of claims 1 to 6, characterized in that it contains a modified rosin (c) and a filler (d) in addition to (a) and the pigment (b). Composition. 8 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic ester
Claims 1 to 7 characterized in that the pigment (b) contains 2 to 200 parts by weight and the rosin modified product (c) 10 to 1000 parts by weight per 100 parts by weight of (a).
Any composition for hot-melting traffic paint. 9 Aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic acid ester
The heat treatment according to any one of claims 1 to 8, characterized in that it contains 2 to 200 parts by weight of pigment (b) and 50 to 1000 parts by weight of filler (d) per 100 parts by weight of (a). Composition for melt type traffic paint. 10 Per 100 parts by weight of aromatic hydrocarbon resin or its modified product with maleic anhydride or maleic acid ester (a), 2 to 200 parts by weight of pigment (b), 10 to 1000 parts by weight of rosin modified product (c) and a filler (d) in an amount of 50 to 1000 parts by weight. 11. The hot-melt traffic paint composition according to any one of claims 1 to 10, characterized in that titanium white or zinc white is used as the pigment (b).