JPH05239308A - Petroleum resin powder and its production - Google Patents

Abstract

PURPOSE:To obtain petroleum resin powder or resin powder consisting essentially of a petroleum resin, having good powdered state, good in storage stability and excellent in mixing property with aggregates and pigments. CONSTITUTION:100 pts.wt. calcium carbonate having 0.1mum particle diameter is added to 900 pts.wt. water in which 1 pts.wt. copolymer having 13000 average molecular weight and obtained by copolymerizing acrylic acid with a polyethylene glycol methacrylate in 1:1 ratio and neutralizing the resultant copolymer with ammonia is dissolved, and the mixture is filtered, dehydrated and dried to produce amphiphatic particles. 15 pts.wt. of the resultant particles are suspended in 100 pts.wt. water and temperature of the suspension is kept at 60 deg.C under stirring. 100 pts.wt. petroleum resin controlled to 400 rate of penetration by mixing oils and fats thereto is heated to 140 deg.C and mixed and emulsified with equivalent amount of the above-mentioned suspension to afford the emulsion. An aqueous solution of polyvinyl alcohol is added to the emulsion so as to give 8% solution based on the solid content of the emulsion and the mixture is dried to provide fine powder of petroleum resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention emulsifies a so-called petroleum resin obtained by polymerizing mainly C ₅ or C ₉ fraction, which is an unsaturated hydrocarbon obtained by decomposing petroleum, and further pulverizes it. It is intended to provide a petroleum resin powder that is streamlined for storage, packaging, transportation, etc. and is convenient to use. It is expected that new petroleum resin powder and its manufacturing method are expected to expand demand and develop new applications. It is related.

[0002]

2. Description of the Related Art Asphalt (bituminous material) is a material that is produced naturally and has been used in many fields. Most commonly used at present are petroleum asphalt.

[0003] Asphalt is used for road pavement, water irrigation work, waterproofing work, electric insulation material, various coating materials, etc., due to its cheapness, adhesive strength, bonding strength, waterproofness, vibration damping property and electric insulation property. However, since asphalt is dark brown or black, its application range is limited.

On the other hand, unsaturated hydrocarbon fractions produced simultaneously with ethylene, propylene, aromatic hydrocarbons and the like during naphtha decomposition in petrochemicals, specifically aliphatic C ₅ fractions and aromatic C ₉ fractions. Distillates, or so-called petroleum resins polymerized mainly from a combination of these are light to almost colorless, so floor binders, paints, adhesives,
It has come to be used in various fields such as printing ink, sizing agent, rubber processing, and traffic paint.

In recent years, there has been a strong demand for harmony with nature and the surrounding environment of townscapes in road pavement, and colored pavement materials using the above-mentioned petroleum resin have been developed. It has come to be used for various purposes, including roads and shopping streets, and even general roads.

In the case of such a colored pavement, gravel having a different particle size is mixed in an appropriate ratio, and powder such as stone powder, petroleum resin, pigment, etc. are mixed and heated, and then sprayed at a predetermined place, It is constructed by spreading. Since the petroleum resin used as a binder here has a high melting point (softening point), in order to coat the aggregate particles uniformly and to effectively bond and fix each other, high temperature until an appropriate viscosity is reached. Must be maintained and used.

Further, from the viewpoint of workability such as transfer in a plant, mixing and stirring, efficiency, etc., it is necessary to always store in a heated and molten state, and for transportation, it is necessary to use a tank truck having a heating device.

In order to eliminate these difficulties and facilitate handling, a light-colored asphalt emulsion prepared by adding a softening agent or the like to a petroleum resin to adjust the penetration and adhesiveness and emulsifying with an emulsifier is used. However, there is a problem that it takes a long time to construct the product because the film formation and adhesion are completed only after the deterioration of physical properties due to the influence of added emulsifiers and stabilizers and the removal and evaporation of water. ..

On the other hand, while treatment such as heating and melting is no longer necessary, since the solid content concentration in the emulsion is about 50 to 60%, approximately the same amount of water as the resin content is stored or transported at the same time. As a result, storage equipment and transportation costs have increased.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the above problems in the prior art, and provides a petroleum resin powder which is easy to handle, store and transport and does not affect the properties of petroleum resin, and a method for producing the same. The purpose is to provide.

[0011]

Means for Solving the Problems The inventors of the present invention firstly reduced the physical properties of petroleum resin emulsions due to forced emulsification by using a large amount of conventional additives such as surfactants and stabilizers. Research focused on emulsifying petroleum resin using inorganic particles (called amphiphilic particles) that have both hydrophilicity and lipophilicity in order to prevent and produce emulsions that are easy to handle and have excellent physical properties. As a result of repeated stacking, appropriate selection of amphipathic particles, mixing ratio with petroleum resin, emulsification conditions such as temperature and pH, selection of emulsifying equipment, etc., can be used to effectively produce a soapless petroleum resin emulsion. In addition to the above finding, the inventors have found that a petroleum resin dry powder having excellent utility value can be produced from this petroleum resin emulsion, and have reached the present invention.

Petroleum resins are roughly classified into aliphatic type, aromatic type, aliphatic / aromatic copolymerization type, aliphatic / alicyclic copolymerization type, cyclopentadiene type, and hydrogenated type resins obtained by hydrogenating these. are categorized.

These petroleum resins are rarely used alone, and are often mixed with other resins, fats and oils, etc. to adjust the physical properties according to the purpose. Although any of these resins can be used in the present invention, particularly in the case of pulverization, they are effectively used as a petroleum resin having a low (soft) softening point or a resin containing petroleum resin as a main component.

If the softening point is high, it is possible to make the resin agglomerated coarse particles to a certain degree by adding a conventional crushing action, but as the softening point becomes lower, it becomes more difficult. Is coming. According to the present invention, it is possible to miniaturize even a very soft resin having a softening point of 50 ° C or lower. Furthermore, the average particle size is about 20 to 3
Since it is possible to obtain a powder of 0 micron,
It has excellent mixability with aggregates and can reduce the heat capacity when heated and melted.

The amphipathic particles used in the present invention are obtained by treating hydrophilic inorganic particles with a hydrophobizing agent or a polymer substance to impart an affinity to both water and an organic solvent. Whether or not it has a property can be known by whether or not it collects at the interface between water and the organic solvent when added and mixed in a mixture of water and the organic solvent and allowed to stand.

The base material of the amphipathic particles used in the present invention is a hydrophilic inorganic particle and includes a substance which is hardly soluble or insoluble in water and is substantially insoluble in water. Examples of such substances include oxides such as silicon dioxide, alumina and titanium dioxide, heavy or light calcium carbonate,
Examples thereof include carbonates such as magnesium carbonate, silicates such as kaolin, clay and talc, hydroxides such as aluminum hydroxide and magnesium hydroxide, and sulfates such as barium sulfate and calcium sulfate.

These inorganic materials are usually used alone to make them amphipathic, but they may be used in combination of two or more kinds. Alternatively, after making them amphiphilic, they are used by mixing two or more kinds. You can also However, considering the particle size of the industrially available inorganic materials and the like, the substantially particularly preferable materials are silicon dioxide, calcium carbonate, talc and the like.

When emulsifying a petroleum resin using amphipathic particles, there is generally a correlation between the particle size of the amphipathic particles used and the particle size of the produced petroleum resin emulsion, and the amphiphilic property is As the particle size of the particles increases, the particle size of the resin of the generated emulsion also increases.

When emulsifying a petroleum resin, it is necessary to use as small an amphipathic particle as possible in view of the need to ensure stability such that sedimentation or aggregation does not occur during long-term storage of the emulsion. Is. For this purpose, it is necessary to use a hydrophilic material having a particle size of 0.6 μm or less for producing the amphipathic particles. Inorganic particles are used.

Since an inorganic layer of amphiphilic particles is formed on the surface of the resin particles in the emulsion obtained by using the amphiphilic particles, the fusion and coalescence of the dispersed resin particles are inhibited.
It helps stabilize the emulsion.

However, when these emulsions are further dried to produce a dry powder, it is not necessary to consider the long-term stability of the emulsion substantially, and the petroleum resin is emulsified in water by the amphiphilic particles, or Any amphipathic particles having a particle size that can be suspended can be used, and even amphipathic particles produced using an inorganic material of about 5 microns can be suspended. If larger particles are used, the average particle size of the petroleum resin in the suspension will be 100 microns or more, and phenomena such as sedimentation and agglomeration of the suspension will occur, resulting in a marked deterioration in stability. It is necessary to use an inorganic material having a particle size of 5 microns or less for producing the medium particles.

Further, as the amount of the amphiphilic particles used for emulsifying the petroleum resin decreases, the stability of the resulting emulsion tends to decrease. For emulsions that must ensure long-term stability, it is necessary to add 20% by weight or more to the petroleum resin. If added in excess of 40% by weight, the viscosity of the emulsion will remarkably increase. 25-3
5% by weight is preferred. When pulverizing, it is not necessary to consider the long-term stability substantially like the limitation of the particle size of the amphipathic particles, so that the content may be 20% by weight or less. Suspension is possible even with about 3% by weight, but in practice it is preferable to add 5 to 35% by weight.

It is important that the lipophilic substance used for surface modification of the hydrophilic inorganic material is a substance that forms a hydrophobic portion on the surface of the inorganic particles, such as a silane compound or a titanate coupling agent. An oil-soluble polyamine condensate such as a dimer acid-polyamine condensate, or an acrylic acid-based polymer such as a copolymer of polyethylene glycol (meth) acrylate and (meth) acrylic acid or fumaric acid, or a copolymer thereof, Homogenol L
Examples thereof include oil-soluble anionic surfactants such as -18 (manufactured by Kao Corporation), and these may be used alone or in combination of two or more components.
The amount of lipophilic substance used is 0.0 with respect to the hydrophilic inorganic material.
It is preferable to add 5 to 2.0% by weight.

When a dry powder is produced from a suspension of a petroleum resin obtained by using amphiphilic particles, it is exposed to a high temperature to evaporate water. Will ooze out from the gaps between the amphiphilic particles covering the surface, resulting in fusion between the particles.

Therefore, in the present invention, prior to drying, a water-soluble polymer such as gum arabic, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, or a partial saponification product of polyvinyl acetate, carboxymethyl cellulose, etc. is previously prepared in the amphiphilic particle emulsion. A powder can be easily obtained by adding an appropriate amount of the compound to petroleum resin and drying.

The type and amount of the water-soluble polymer compound affect the film thickness and affect the performance such as strength of the obtained powder. Therefore, the type and amount of the water-soluble polymer compound may be selected according to the desired performance such as strength. To coat the surface of the petroleum resin dispersed particles coated with the amphiphilic inorganic particles, 1% by weight or more is necessary with respect to the solid content of the emulsion, the solid content of the emulsion is 40 to 50% by weight, and the average particle size is Is 2
In the case of a 0 to 30 micron suspension, an addition amount of about 5 to 15% by weight is preferable.

As described above, a stable petroleum resin emulsion can be obtained by emulsifying a petroleum resin using the amphipathic particles. Further, a small amount of these water-soluble polymer compounds is added and dried with a spray dryer or the like. By drying with a device, even a soft petroleum resin having a large penetration can be pulverized.

[0028]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. In addition, a part shows a weight part in an Example.

Example 1 100 parts of calcium carbonate (mean particle size: 0.1 micron) was copolymerized by a conventional method at a ratio of acrylic acid and polyethylene glycol methacrylate 1: 1 and neutralized with ammonia. After adding 1 part of a copolymer having an average molecular weight of 13,000 to 900 parts of dissolved water and thoroughly stirring with a disper to allow the copolymer resin to adhere to the surface of calcium carbonate, filtration with a filter press and dehydration were carried out. And amphipathic particles were produced by the method.

Amphiphilic particles 15 thus produced
Parts are suspended in 100 parts of water, and the temperature is kept at 60 ° C. while thoroughly stirring with a disper. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C.
Then, both were passed through the Haller homogenizer and mixed and emulsified in the same amount.

An aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Gohsenol GH-17) having a saponification degree of about 88%, which had been adjusted to 10% in advance, was added to the emulsion to obtain a solid content in the emulsion. On the other hand, polyvinyl alcohol was added to 8% so that it was dried with a spray dryer (Okawara Kakohki: FOC-25) under a hot air inlet temperature of 150 ° C and an outlet temperature of 100 ° C with sufficient stirring to obtain petroleum oil. A fine dry powder of resin was obtained.

Example 2 100 parts of calcium carbonate (average particle size: 0.5 micron) was added to a solution prepared by dissolving 1 part of a condensate of dimer acid and polyamine (Fuji Kasei Kogyo Co., Ltd .; trade name Tomeide 296) in 60 parts of dichloromethane. Then, after sufficiently stirring, the solvent was distilled off by heating to produce amphiphilic particles.

15 parts of the particles are suspended in 100 parts of water, and the temperature is kept at 60 ° C. while sufficiently stirring with a disper. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

An aqueous solution of hydroxyethyl cellulose (for example, Natrozol 250LR manufactured by Hoechst Synthetic Chemical Industry Co., Ltd.) adjusted to 10% in advance in this emulsion was used as hydroxyethyl cellulose based on the solid content in the emulsion. It was added to 8% and dried with a freeze dryer (Tokyo Rika Kikai Co., Ltd .: FD-5N) under the conditions of a trap temperature of -50 ° C. and a vacuum degree of 5 × 10 ⁻³ Torr. A fine dry powder was obtained.

Example 3 Calcium carbonate (average particle size 3.0 μm) was used in Example 2
The amphiphilic particles were produced by the same treatment as described above.

15 parts of the particles are suspended in 100 parts of water, and the temperature is kept at 60 ° C. while sufficiently stirring with a disper. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

An aqueous solution of polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Gohsenol GH-17) having a saponification degree of about 88%, which had been adjusted to 10% in advance, was added to the emulsion, based on the solid content of the emulsion. Added as a polyvinyl alcohol to 8%, and as a coloring pigment, ferric oxide (manufactured by Titanium Industry: Mapico Red R-110A)
Was added by 2% and dried with a spray dryer in the same manner as in Example 1 with sufficient stirring to obtain a red fine dry powder of petroleum resin.

Comparative Example 1 15 parts of amphipathic particles prepared by the same manner as in Example 1 were prepared using calcium carbonate (average particle size: 6.0 μm) in 100 parts of water.
Part, and while stirring well with a disper, raise the temperature to 6
Keep at 0 ° C. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

Comparative Example 2 Calcium carbonate (average particle size 0.5 micron) was suspended in 3 parts of amphipathic particles prepared in the same manner as in Example 1 in 100 parts of water, and the temperature was maintained while sufficiently stirring with a disper. 60
Keep at ℃. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

COMPARATIVE EXAMPLE 3 Calcium carbonate (average particle size: 0.5 micron), 20 parts of amphipathic particles produced in the same manner as in Example 1 was added to 100 parts of water.
Part, and while stirring well with a disper, raise the temperature to 6
Keep at 0 ° C. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

Polyvinyl alcohol having a saponification degree of about 88%, which was adjusted to 10% in advance in this emulsion (for example, Gohsenol GH-1 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
7) The aqueous solution was added so as to be 2% as polyvinyl alcohol with respect to the solid content in the emulsion, and the hot air inlet temperature was 150 ° C. at the outlet with a spray dryer (FOC-25 manufactured by Okawara Kakohki) with sufficient stirring. It was dried at a temperature of 100 ° C. to obtain a petroleum resin fine dry powder.

Comparative Example 4 Calcium carbonate (average particle size: 0.5 micron) was prepared in the same manner as in Example 1 except that 30 parts of amphiphilic particles were mixed with 100 parts of water.
Part, and while stirring well with a disper, raise the temperature to 6
Keep at 0 ° C. On the other hand, 100 parts of a petroleum resin mixture prepared by mixing oils and fats with a penetration of 400 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Harrell homogenizer.

This emulsion was dried with a spray dryer (FOC-25, manufactured by Okawara Kakohki Co., Ltd.) under sufficient conditions of a hot air inlet temperature of 150 ° C. and an outlet temperature of 100 ° C. while sufficiently stirring to obtain a fine dry powder of petroleum resin. ..

The finely powdered state of the petroleum resin fine powders of Examples 1 to 3 and Comparative Examples 3 and 4 was examined, and the emulsions of Comparative Examples 1 and 2 were tested for emulsion state and emulsion stability. The results are shown in Table 1.

[0045]

[Table 1]

(Note 1) The evaluation of the emulsified state was evaluated as ◯ when spherical petroleum resin particles were dispersed in water and passed through a 2m / m-th sieve and there was no residue. (Note 2) 100 ml of emulsion was placed in a 100 ml graduated cylinder, and the state of separation of the aqueous layer was observed and evaluated when it was left in a room at 20 ° C for 7 days. For example, those that returned to the emulsified state were marked with Δ, and those that did not return to the emulsified state with stirring were marked with x. (Note 3) The evaluation of the powdered state was evaluated as ○ when the residue was 5% or less and the residue was 5% or less.

The petroleum resin or the powder containing petroleum resin as the main component of the present invention is mixed in a suitable proportion with a mixture of powders such as gravel and stone powder having different particle diameters, pigments and the like in a proportion of 5 to 10%. It can be constructed by heating the mixed material or by spraying it at a predetermined place without heating and applying pressure.

[0048]

According to the present invention, the powdered state is good,
Therefore, it is possible to obtain a powder of petroleum resin or a resin containing petroleum resin as a main component, which has good storage stability and excellent mixability with aggregates and pigments.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Yamashita 1-27-4 Shimorenjaku, Mitaka City, Tokyo (72) Inventor Isao Sekiguchi 2-26-9 Seigaoka, Tama-shi, Tokyo (72) Yoshio Iwasaki Tokyo 2-30-10 Sanno, Ota-ku

Claims (2)

[Claims] 1. A water-soluble polymer is coated on the outside of petroleum resin or resin particles containing petroleum resin as a main component, which are coated with amphiphilic inorganic particles produced from inorganic particles having a particle size of less than 5 microns. Petroleum resin powder characterized by. 2. A petroleum resin obtained by rapidly stirring suspension water of amphipathic inorganic particles produced from inorganic particles having a particle size of less than 5 microns and heat-melted petroleum resin or a resin containing petroleum resin as a main component. A method for producing a petroleum resin powder, which comprises adding 1% by weight or more of a water-soluble polymer substance to an emulsion, based on the solid content of the emulsion, and then drying.