JPS5974154A - Petroleum resin emulsion and emulsion composition consisting of said emulsion and latex - Google Patents

Abstract

PURPOSE:To provide a petroleum resin emulsion suitable for use as a paving material and having excellent stability, water resistance, adhesion, etc., by adding a surfactant and water to a petroleum resin obtd. by the oxidative polymn. of a fraction which is particularly rich in arom. component among petroleum fractions. CONSTITUTION:A petroleum fraction having an average MW of 200-800 is extracted with furfural, phenol or a similar solvent to obtain a fraction rich in aromatics. The resulting fraction is catalytically reacted with an oxygen-rich gas or a gas contg. oxygen and ozone at 200-380 deg.C to produce a petroleum resin. 30-90wt% said petroleum resin, 1-6wt% surfactant and 10-60wt% water are thoroughly mixed together in a colloid mill to obtain the desired petroleum resin emulsion. Pref. a latex is further blended with this emulsion, and the resulting composn. is used as a material for use in the production of paving materials, paints, etc.

Description

Detailed Description of the Invention This invention relates to a petroleum resin emulsion, more specifically, a petroleum resin emulsion obtained by oxidative polymerization of a petroleum fraction particularly rich in aromatic components, and a petroleum resin emulsion obtained from the emulsion and latex. The present invention relates to an emulsion composition.

Conventionally, attempts have been made to convert crude oil residues into so-called ASF7/reto emulsions, and this has already been put to practical use. That is, in order to improve various properties of Asphalt 7/RETO, such as softening at high temperatures, embrittlement at low temperatures, and low adhesive strength, asphalt is emulsified and mixed into a rubber emulsion (latex).

Asphalt is a high-molecular polymer mixture with a complex structure, as is well known, and therefore the emulsions obtained from it have low stability (and are difficult to store for long periods of time) and have a low aromaticity index fa ( 0.2 to 0.3), low dispersibility with reinforcing agents such as carbon black, insufficient compatibility with the rubber components in latex, and problems with coating films obtained from emulsions containing latex. It has drawbacks such as insufficient mechanical and chemical properties.

The present invention provides a petroleum resin emulsion that eliminates all the drawbacks of the above-mentioned asphalt emulsions. In other words, the petroleum resin emulsion of the present invention has an aromaticity index close to that of tar-based emulsions, does not contain carcinogenic substances such as 3,4-petsupyrene, and is stable for a much longer period of time than asphalt emulsions. It has excellent characteristics such as good storage stability, good dispersibility of the reinforcing agent, and good compatibility with the rubber component in the latex, resulting in a coating film with excellent physical and chemical properties. .

The applicant has already reported that a gas containing oxygen or a gas containing oxygen and ozone, such as a distillate rich in aromaticity extracted from a petroleum fraction with an average molecular weight of 200 to 800 using furfural, phenol, or a similar solvent, We have developed a petroleum resin obtained by catalytic reaction at a temperature of 200 to 380°C, and have applied for a patent for its use in coke manufacturing binders, paving agents, paints, rubber compositions, etc. (Japanese Patent Publication No. 54-26241) , Japanese Patent Publication No. 55-139488, Japanese Patent Publication No. 56-43266.

JP-A No. 55-139440). Such petroleum resin does not contain carcinogens such as 3,4-pentsupyrene.

By selecting polymerization conditions, the softening point can be changed from low to high softening point (
O~120'O) can be easily obtained, and it has excellent compatibility with polymer compounds used as components of paints and rubbers, so it can be used for the uses described in the above patent application. It is possible.

This invention is based on the discovery, previously developed by the applicant, that the above-mentioned petroleum resin has extremely good emulsion stability when emulsified.

In the case of asphalt, it is known that using a cationic surfactant as a surfactant can create a strong film layer in a short time and provide excellent water resistance (Japanese Patent Publication No. 48-109).
(See No. 39). However, as mentioned above, anionic surfactants are generally used in latexes that are blended into asphalt emulsions to improve the drawbacks such as softening at high temperatures, embrittlement at low temperatures, and low adhesive strength. The reality is that when a latex is blended into an asphalt emulsion, a complicated operation is required to convert the anionic nature of the latex to cationic nature immediately before use.

The petroleum resin of the present invention is extremely stable even when anionic surfactants are used. It also has the advantage that it does not require any special operations, and that it adheres strongly to wet surfaces even when anionic surfactants are used.

The petroleum resin emulsion of the present invention contains about 30% of the petroleum resin described above.
The basic constituents are ~90% by weight, about 1-6% by weight of surfactant, and 10-60% by weight of fishing rod, and if desired, up to about 40% by weight of additives commonly used in this formulation. Can be added. Further, when using a petroleum resin with a high softening point (approximately 80 to 120° C.), it is preferable to use up to approximately 20% by weight of a solvent based on the Rhea resin to solubilize the resin prior to emulsification.

The petroleum resin which is a component of the petroleum resin emulsion of the present invention is an aromatic fraction extracted from a petroleum fraction with an average molecular weight of 200 to 8,000 using furfural, phenol, or a similar solvent, and contains oxygen. It is obtained by contact reaction with a gas or a gas containing oxygen and ozone at a temperature of 200 to 380'O. In this case, the reaction time depends on the oxygen (oxygen) concentration, reaction temperature, raw materials, reaction type (continuous type,
Although it cannot be generalized because it varies depending on the type (batch type, etc.), 20 minutes to 100 hours is usually appropriate. The reaction is related to the softening point (as7arte/content number in the resin).

) reaches the desired value. That is, the reaction is terminated when the asphalte/content in the resin reaches a desired value of 10% or more, preferably 30% or more. In this way, the softening point can be increased from 0'C to 120
Any petroleum resin can be produced with ℃.

In the present invention, the surfactant is cationic.

Anionic and nonionic surfactants are used.

Cationic surfactants include quaternary ammonium salts, such as long-chain primary ammonium salts, alkyltrimethylammonium salts, dialkyldimenalammonium salts, alkyldimethylethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, Alkylaminoethyl diethylamine salt etc.; quaternary ammonium salt having an ester bond amine and an ether bond;
For example, stearooquin methylpyridinium salt, fatty acid triethanolamine, trioxyethylene fatty acid triethanolamine, fatty acid diptylaminoethanol, etc.;
Heterocyclic amino/, e.g. alkyl betaine IJ 7.1-
Hydroxy/ethyl-2-alkylimidazoli/, 1-acetylaminoethyl-2-alkylimidacillin, etc.; Amine derivatives 1 such as polyoxyethylene alkylamine, N-alkylpropylene diamine, N-alkyl polyethylenenoamine, N- Examples include alkylpolyeterenopolyaminone methyl sulfate, long-chain amino oxide, and the like.

Examples of anionic surfactants include fatty acid derivatives such as fatty acid soap, sodium abietate, naphthenic acid soap, fatty acid sarcosides; sulfate ester type surfactants 1 such as long-chain alcohol sulfate salts, olefinosulfate salts, fatty acid ethylene Collido sulfate salt, polyoxyethylene alkyl ether sulfate salt, polyquinoethylene alkyl phenyl ether sulfate salt + fatty acid monodaliseride sulfate salt, fatty acid alkyl sulfate salt, fatty acid amide sulfate salt.

Fatty acid monoalkanolamide sulfate ester salts, etc.; sulfonic acid type and phosphoric acid ester type surfactants 1 such as alkanosulfonates, petroleum sulfonates, α-olefin sulfonic acids, α-sulfo fatty acid salts, alkyl sulfo acetates, dialkyl Sulfo(acid), monoalkyl sulfosuccinate, lower alkylnaphthalene sulfonic acid,
Lower dialkylnaphthalinosulfonate/acid, alkylphenol sulfonate, lidanine sulfonate, alkylbenzene sulfonate.

Examples include alkyl phosphate ester salts, polyoxyethylene alkylphenol ether phosphate ester salts, and polyoxy7-ethylene alkyl ether phosphate ester salts.

Examples of nonionic surfactants include polyoxyethylene surfactants, such as polyoxyethylene algyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl 7-methyl ethyl, polyoxyethylene abiethyl alcohol, and holoxy. Ethylene alkylnaoether, polyoxyethylene alkylamide, polyoxyetherene-polyoxopropylene glycol, polyoxyethylene monofatty acid ester, polyoxyethylene difatty acid ester, polyoxyethylene sorbitan monofatty acid ester, polyoxyethylene sorbitan monofatty acid esters, polyoquinoethylene sorbitan trifatty acid esters, etc.; polyhydric alcohol and alkylolamide surfactants, such as ethylene glycol monofatty acid esters, glopylene glycol monofatty acid esters, diethylene glycol monofatty acid esters, glycerin/monofatty acid esters, Examples include taerythritol monofatty acid ester, solpidan monofatty acid ester, /yosaccharide fatty acid ester, fatty acid monoethanolamide, fatty acid jetanolamide, and the like. In the present invention, amphoteric surfactants such as N-alkyl tridarynes and alkyl betaines can also be used.

Rue, commonly used calcium carbonate ditalc, bentonite, and clay as additives.

Inorganic fillers such as glass flakes, inorganic pigments such as titanium, red iron oxide, and chromium oxide, organic pigments, plasticizers, stabilizers (antioxidants, etc.), and the like can be used.

Production of the petroleum resin emulsion of the present invention 1. General method 2. For example, a predetermined amount of petroleum resin catfish is heated to an appropriate temperature to melt it, a predetermined amount of surfactant is added, and the surfactant is put into an emulsifier. After stirring until the mixture is sufficiently divided, a predetermined amount of hot water is gradually added while stirring, and if necessary, additives such as extender pigments are added. When the softening point of the petroleum resin is high (approximately 80-120'C), it is advantageous to use up to about 20% by weight of solvent, based on the resin. The solvents used in this case are benzene,
It is a 0T bath solvent for aromatic hydrocarbons such as toluene and xylene, mineral turpentine and other resins.

It is also possible to speed up the drying time of the petroleum resin emulsion by adding a lower alcohol (methanol, ethanol, etc.).

The petroleum resin emulsion according to the present invention can be used alone or mixed with other emulsions for a wide range of applications as an alternative to an asphalt emulsion. For example, building materials, road paving materials, paints, adhesives, caulking materials,
It can be used as a tooling material, soil improvement stabilizer, etc.

The petroleum resin emulsion of the present invention has good emulsion stability (and the petroleum resin films obtained by applying it to various base materials have good adhesion to the base material) and have very good drying properties, so the film thickness can be reduced. Compared to conventional asphalt emulsions, it can be made much larger (film thickness of multiple coatings, asphalt-based, about 5 times the present invention), and its physical and chemical properties are also extremely superior. The petroleum resin itself, which is a component of the petroleum resin emulsion of It is expected that a rubber emulsion, that is, an emulsion obtained by blending latex, will exhibit excellent properties.

This was as expected by L.L. Namely, natural rubber latex and SBR latex, BR latex, butyl rubber latex, EPR latex, EVA
It has been confirmed that the blended emulsion of synthetic rubber latex such as latex, NBR latex, CR latex, acrylic latex and the petroleum resin emulsion of the present invention exhibits even better properties. In other words, the coating film obtained by applying the blended emulsion to the base material has a completely uniform mixture of petroleum resin and rubber components, and the physical and chemical properties of the resulting film are further improved. Anionic surfactants are generally used in latex, and anionic surfactants can also be used to form the petroleum resin emulsion of the present invention, so the two can be easily mixed in any ratio. It can be easily used as a blended emulsion. This point is one of the major advantages of the present invention compared to asphalt emulsions which need to be formulated to be cationic. Of course, the properties of the obtained membrane are much better in the petroleum resin emulsion of the present invention than in the case of asphalt emulsion.

Next, the petroleum resin emulsion of the present invention will be explained with reference to Examples.

Example Production of petroleum resin emulsion ■ Petroleum resin FR-40 manufactured by Fuji Kosan Co., Ltd. (softening point 40°C)
Heat 50 parts of petroleum resin) to about 80°C to melt it, and add alkylbenzene sulfo/acid to it.
Part by weight was added and thoroughly mixed with a homogenizer, and 50 parts by weight of hot water was gradually added to obtain a petroleum resin emulsion.
child.

■ Petroleum resin FR-100 manufactured by Fuji Kosan (softening point 100)
'Q Petroleum Resin) 40 tonne part is melted to about 150"C,
Add 10 parts of mineral turpentine to this and raise the temperature to about 80°C.
To this, add 3 parts by weight of higher alcohol sulfate ester salt and mill in a colloid mill (after mixing,
Gradually add 50 parts by weight of hot water to make petroleum resin emulsion 6.
Obtained.

■ Petroleum resin FR-80 manufactured by Fuji Kosan (softening point 80°C)
60 parts by weight of petroleum resin) was heated to about 150°C and melted in a bath, 4 parts of γ-lkylamine salt was added thereto and stirred well, then 40 parts by weight of hot water (about 80'C) was gradually added. A petroleum resin emulsion was obtained.

IV? Fiji Kosan Co., Ltd. petroleum resin FR-80 (softening point 80
'0) Heat 40 parts to approx.]50°C to melt it, add 2 parts by weight of sorbitan fatty acid ester (mix it,
Next, 30 parts by weight of hot water was gradually added to obtain a petroleum resin emulsion.

The typical manufacturing method of the petroleum resin emulsion of the present invention has been explained above in t to For straight ass 7A/L=) (softening point 48°0),
Table 1 shows the results of examining the emulsion stability of Fluono Asphald (softening point 90''C) using the same anionic, cationic, and nonionic surfactants 41.

Emulsion composition with latex v Commercially available CR (chlorobreno rubber) latex, 5
BR (Style/)゛Tadiene Rubber Latex
and AC (acrylic) latte.

30 parts by weight of each latex and 15 parts of the petroleum resin emulsion obtained in step (1) above (heavily sewn).

20 parts by weight of an extender pigment (manufactured by Nippon Talc Co., Ltd., Nippon Talc) were thoroughly mixed to obtain an emulsion composition. This composition was applied onto a material to be coated and dried to obtain a coating film. Table 2 shows the measured object values.

Og
2) 2-ball 4850A manufactured by Nippon Zeon Co., Ltd. 3) Primal M4 manufactured by Nippon Acrylic Chemical Co., Ltd. The test was carried out in accordance with JIS K6911 with a film thickness of 3u.

5) A film thickness of 0.2N was also accepted and was carried out in accordance with JI8 5400.

6) Tested using an adhesive tester manufactured by Elcometer.

Claims (1)

[Scope of Claims] l A fraction rich in aromaticity extracted from a petroleum fraction with an average molecular weight of 200 to 800 with furfural, phenol, or a similar solvent is mixed with a gas containing oxygen or a gas containing oxygen and ozone. A petroleum resin emulsion whose basic constituents are about 30 to 90% by weight of petroleum resin obtained by catalytic reaction at a temperature of 200 to 380'O, about 1 to 6% by weight of a surfactant, and about 10 to 60% by weight of water. 2 An aromatic fraction extracted from a petroleum fraction with an average molecular weight of 200 to 8,000 with furfural, phenol, or a similar solvent, a gas containing oxygen or a gas containing oxygen and ozone, and a temperature of 200 to 380°C. An emulsion composition consisting of a petroleum resin emulsion and latex as basic constituents: about 30 to 90% by weight of petroleum resin, about 1 to 6% by weight of surfactant, and about 10 to 60% by weight of water. thing. 3. The emulsion composition according to claim 2, wherein the surfactant is an anionic surfactant.