JPH05239307A - Petroleum resin emulsifier and its production - Google Patents

Abstract

PURPOSE:To obtain a petroleum resin emulsifier by dispersing petroleum resin particles coated with amphiphatic inorganic particles in water. CONSTITUTION: 100 pts.wt. calcium carbonate having 0.1mum average particle is added to 900 pts.wt. water in which 1 pts.wt. copolymer having 13000 average molecular weight and obtained by copolymerizing an acrylic acid with a polyethylene glycol methacrylate and neutralizing the resultant copolymer with ammonia is dissolved, and the mixture is sufficiently stirred so as to give particles in which the copolymer is attached to the surface of calcium carbonate and these particles are filtered, dehydrated and dried. 25 pts.wt. these particles are suspended in 100 pts.wt. water and temperature of the suspension is kept at 60 deg.C under stirring. On the one hand, 1000 pts.wt. petroleum resin mixture obtained by mixing oils and fats in a petroleum resin so as to adjust 400 rate of penetration is heated at 140 deg.C. Then, equivalent amounts of the petroleum resin mixture and the above-mentioned suspension are charged to a homogenizer to provide the objective petroleum resin emulsifier.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to heating a so-called petroleum resin obtained by polymerizing mainly C ₅ or C ₉ fraction which is an unsaturated hydrocarbon obtained by decomposing petroleum, or a resin containing the resin as a main component. It is an emulsion that can be used at room temperature without melting, streamlines storage, packaging, transportation, etc., and provides a petroleum resin emulsion that is convenient to use, and is expected to expand demand and develop new applications. The present invention relates to a novel petroleum resin emulsion and a method for producing the same.

[0002]

2. Description of the Related Art Asphalt (bituminous material) is a material that is naturally produced and has been used in many fields. Most commonly used 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, even in road pavement, there has been a strong demand for harmony with nature and the surrounding environment such as townscapes, and colored pavement materials using the above-mentioned petroleum resin have been developed. It has come to be used for various purposes such as cycling roads, shopping streets, and even general roads.

In the case of such a colored pavement, gravel having different particle diameters are mixed in an appropriate ratio, and powder such as stone powder, petroleum resin, pigment, etc. are mixed and heated, and sprayed at a predetermined place, It is constructed by spreading. The petroleum resin used as a binder here has a high melting point (softening point), so that in order to coat the aggregate particles uniformly and to effectively bond and fix each other, it is necessary to increase the temperature to an appropriate viscosity. 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 melted state, and it is necessary to use a tank truck having a heating device for transportation.

In order to eliminate these difficulties and facilitate handling, a light-colored asphalt emulsion prepared by adding a softening agent or the like to petroleum resin to adjust the penetration and adhesiveness and emulsifying with an emulsifier is used. However, due to the effects of added emulsifiers, stabilizers, etc., it is unavoidable that performances such as dryness and water resistance deteriorate.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above problems in the prior art and is an amphiphilic inorganic particle which is easy to handle, store and transport and does not affect the properties of petroleum resin. Another object is to provide an emulsifier obtained by coating a resin containing petroleum resin as a main component and a method for producing the same.

[0009]

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. That is, the present invention has been reached and the present invention has been reached.

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

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

[0012] 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, in consideration of the particle size of the industrially available inorganic materials, the substantially particularly preferable materials are silicon dioxide, calcium carbonate, talc and the like.

When emulsifying a petroleum resin using amphipathic particles, there is a correlation between the particle size of commonly used amphipathic particles and the particle size of the produced petroleum resin emulsion. The larger the particle size of, the larger the particle size of the resin of the emulsion produced.

Therefore, when emulsifying a petroleum resin or a resin containing a petroleum resin as a main component by the method of the present invention, it is necessary to ensure stability such that sedimentation or aggregation does not occur during long-term storage of the emulsion. It is also necessary to use amphiphilic particles that are as small as possible. From this point of view, in order to produce amphiphilic particles, it is necessary to use inorganic particles of 0.6 micron or less, and in order to industrially stably supply inorganic particles up to about 0.05 micron. Is 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.

Further, as the amount of the amphipathic particles used for emulsifying the resin decreases, phenomena such as sedimentation and aggregation of the emulsion are likely to occur and the stability tends to decrease. With respect to the emulsion for which long-term stability must be ensured, it is necessary to add 20% by weight or more to the resin, but if 40% by weight or more is added, the viscosity of the emulsion will remarkably increase, so that it is practically 25- 35% by weight is preferred.

It is important that the lipophilic substance used for the 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. , Oil-soluble polyamine condensates such as dimer acid and polyamine condensates, polyethylene glycol (meth) acrylate and (meth)
Acrylic acid-based polymers such as copolymers with acrylic acid or copolymers thereof, homogenol L-18 (manufactured by Kao Corporation)
Oil-soluble anionic surfactants such as
These may be used alone or in combination of two or more. The amount of lipophilic substance used is
It is preferable to add 0.05 to 2.0% by weight to the hydrophilic inorganic material.

As the petroleum resin used in the present invention, the above-mentioned petroleum resin itself, a hydrogenated petroleum resin or a natural resin such as rosin or a petroleum resin blended with oils and fats in order to control the softening point of the petroleum resin is mainly used. What is used as a component or what mixed the pigment etc. can be used.

[0019]

EXAMPLES Hereinafter, the present invention will 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 (average particle diameter 0.1 micron) was copolymerized with acrylic acid and polyethylene glycol methacrylate in a ratio of 1: 1 by a conventional method, 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.

25 parts of the particles are suspended in 100 parts of water, and the temperature is kept at 60 ° C. while being sufficiently stirred 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.

Comparative Example 1 10 parts of amphipathic particles produced in the same manner as in Example 1 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, mixing oils and fats with a penetration of 40
100 parts of the petroleum resin mixture prepared to 0 was heated to 140 ° C., and both of them were mixed and emulsified in the same amount through a Haller homogenizer.

Comparative Example 2 Calcium carbonate (average particle size 0.8 μm) was prepared in the same manner as in Example 1, and 30 parts of amphiphilic particles were added to water 10 parts.
Suspend in 0 part and keep the temperature 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.,
Both of them were mixed and emulsified in the same amount through a Haller homogenizer.

The petroleum resin emulsions obtained in Example 1 and Comparative Examples 1 and 2 and commercially available petroleum resin emulsions were examined for their emulsified state, long-term stability and water resistance. The results are shown in Table 1.

[0025]

[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 2 m / m-th sieve and there was no residue. (Note 2) 100 ml of the emulsifier was put into a 100 ml graduated cylinder, and the separation state of the aqueous layer when left standing in a room at 20 ° C. for 7 days was observed and evaluated. (Note 3) A slate plate that has been treated with an epoxy solvent-based paint to eliminate suction is used as the base plate.
A film thickness of 2 m / m was applied, and one drop of water was dropped on this coating film at regular intervals, and the time until it was strongly rubbed with a fingertip and re-emulsification was stopped was measured.

The emulsion of the present invention is prepared by mixing sanding agents having different particle diameters, powders such as stone powder, pigments, etc. in an appropriate ratio, and mixing the solid content in the emulsion in an amount of 5 to 10% by weight. The mixture can be applied by heating or spreading the mixture at a predetermined place without heating and spreading the mixture.

[0028]

From the results shown in Table 1, it is understood that the petroleum resin emulsion of the present invention has an emulsified state and long-term stability of the emulsion comparable to those of commercially available petroleum resin emulsions, and is excellent in water resistance.

 ─────────────────────────────────────────────────── ─── 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 petroleum resin coated with 20% by weight or more (based on petroleum resin or a resin containing petroleum resin as a main component) of amphiphilic inorganic particles produced from inorganic particles having a particle size of 0.6 micron or less. Alternatively, a petroleum resin emulsion obtained by dispersing resin particles containing petroleum resin as a main component in water. 2. Suspended water and petroleum resin in an amount of 20% by weight or more based on the petroleum resin of the amphiphilic inorganic particles produced from the inorganic particles having a particle size of 0.6 μm or less or the resin particles containing petroleum resin as a main component or A method for producing a petroleum resin emulsion, which comprises mixing a resin containing a petroleum resin as a main component with heating and stirring.