JPH0656493A - Powdery polymer composition containing hydraulic substance and its production - Google Patents

Abstract

PURPOSE:To provide a powdery polymer composition containing a hydraulic substance, good in operating efficiency without causing blocking and having the function to impart the durability to concrete, a repairing material, a flooring material, a waterproofing material and a building material, etc., and a method for producing the flooring material. CONSTITUTION:(1)This powdery polymer composition comprises a synthetic resin and/or a synthetic rubber, a hydraulic substance and a water-reducing agent (and a defoaming agent). Furthermore, (2) the objective method for producing the powdery polymer composition is to premix the water-reducing agent capable of improving the fluidity of a kneaded cement substance (and the defoaming agent capable of reducing the amount of air in the kneaded cement substance) in a synthetic resin emulsion and/or a synthetic rubber latex and simultaneously introduce the resultant synthetic resin emulsion and/or synthetic rubber latex containing the water-reducing agent therein and the hydraulic substance into a spray dryer and spray-dry the resultant mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a powdery polymer composition containing a hydraulic substance, which comprises a synthetic resin emulsion and / or a synthetic rubber latex and a hydraulic substance and has excellent dispersibility. . Further, its industrial application fields are diverse, such as solid and highly durable concrete, repair materials, floor materials, waterproof materials, adhesives and building materials.

[0002]

2. Description of the Related Art Conventionally, synthetic resin emulsions and / or synthetic rubber latex are mixed with cement, aggregate, water and the like to obtain crack resistance, bending strength, impact strength, and mortar resistance. It is known to be used for high-durability mortar and the like with improved adhesive strength. It is also known to obtain a building material by bonding and curing a synthetic hydrate with a synthetic resin emulsion.

On the other hand, by densifying the hardened cement product, it prevents the penetration of harmful gases and chlorine ions, and improves the durability of the hardened cement product. Water reducing agents that reduce the water / cement ratio without damaging them and defoaming agents that reduce the air content of the cement mixture are known.

Under these circumstances, by using a synthetic resin emulsion and / or a synthetic rubber latex in combination with a water reducing agent or a defoaming agent, a hardened cement product which is resistant to cracking and has excellent durability has been studied. There is.

However, when a synthetic resin emulsion and / or a synthetic rubber latex is mixed with cement, a hydration reaction occurs and the mixture hardens. Since synthetic resin emulsions and synthetic rubber latexes are aqueous liquid dispersions, there are problems such as high transportation costs and incorrect measurement on site, so synthetic resin emulsions and / or synthetic It is desired to make rubber latex into a powder form, and various methods for obtaining a powdery polymer having good dispersibility have been studied.

For example, as a method for obtaining a powder from a synthetic resin emulsion such as an ethylene / vinyl acetate copolymer,
By adding 5 to 20 parts by weight of polyvinyl alcohol as a protective colloid to 100 parts by weight of the polymer and polymerizing the monomer component in an aqueous system, the resulting aqueous dispersion of the copolymer is spray-dried. When the average particle size is 0.01 to
0.5 μm of dry anti-blocking material such as aluminum silicate, silica and calcium carbonate is added to the spray dispersion separately from the aqueous dispersion at a ratio of 3 to 30 parts by weight based on 100 parts by weight of the solid content of the aqueous dispersion. A method of spraying simultaneously while introducing is known (Japanese Patent Publication No. 55-50971).

However, these methods are not always sufficient to prevent blocking of the obtained powdery polymers, and there is a problem of workability.

As a result of various studies to solve the above problems, the present inventors have found that when a synthetic resin emulsion and / or a synthetic rubber latex and a hydraulic substance are spray-dried,
Mix the water reducing agent and defoaming agent into the resin and / or rubber in advance,
It was found that blocking simultaneously does not occur by simultaneous drying, and a hydraulic substance-containing powdery polymer composition having excellent workability can be obtained, and the present invention has been completed.

[0009]

That is, the present invention provides a powdery polymer composition containing a synthetic resin and / or synthetic rubber, a hydraulic substance, a water reducing agent and a defoaming agent as a first invention, and Resin emulsion and / or synthetic rubber latex,
When the hydraulic substance is spray-dried, a water-reducing agent and a defoaming agent are mixed in advance with the resin emulsion and / or the rubber latex, simultaneously introduced into a spray dryer, and spray-dried, and the powder containing the hydraulic substance is characterized. A second aspect of the present invention is a method for producing a polymer composition.

The present invention will be described in detail below.

Examples of the synthetic resin emulsion according to the present invention include emulsions of vinyl polymers such as acrylics, vinyl acetates, vinylidene chlorides and vinyl chlorides, and those obtained by copolymerizing two or more of these are also used. It is possible.

Specific examples of the copolymer include, for example, vinylidene chloride / butyl acrylate copolymer, ethylene /
Examples thereof include vinyl acetate copolymers and vinyl acetate / vinyl versatate copolymers, and of these, the use of vinyl acetate copolymer emulsions is particularly preferable from the viewpoint of adhesive strength with the cement hardened product.

In order to improve weather resistance, alkali resistance and water resistance, it is preferable to copolymerize the vinyl acetate synthetic resin with another comonomer.

Examples of these comonomers include cyanated vinyl monomers, unsaturated carboxylic acid monomers, acrylic acid ester monomers, methacrylic acid ester monomers, vinyl ether monomers, amide monomers, maleimide monomers, halogenated olefin monomers and polyfunctional vinyl. Examples thereof include monomers, and it is also possible to use a combination of two or more of these. The amount of these copolymerizable comonomers used is 10 in total of vinyl acetate and comonomer.
20-80 parts by weight is preferable at most with respect to 0 parts by weight, and 2
0 to 50 parts by weight is more preferable. When the amount of the copolymerizable comonomer used exceeds 80 parts by weight, it may be difficult to obtain the excellent adhesiveness inherent to vinyl acetate.

The synthetic rubber latex according to the present invention includes a latex synthesized from a diene monomer,
Examples thereof include styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, methyl methacrylate / butadiene copolymers, and latexes such as polybutadiene and polychloroprene.

The particle size of these synthetic resin emulsions and synthetic rubber latex is preferably about 0.05 to 5 μm.

Examples of the hydraulic substance according to the present invention include those containing a cementitious substance as a main component and / or inorganic ultrafine powder.

Examples of the cementitious substance include various Portland cements such as ordinary Portland cement, early strength Portland cement, super early strength Portland cement and white Portland cement, and these Portland cements include blast furnace slag, silica and fly ash. It is also possible to use mixed cement mixed, ultra-rapid hardening cement, and alumina cement. Here, as the ultra-rapid cement, there is, for example, fluorine-containing calcium aluminate. Further, low heat-generating cement such as moderate heat cement, blast furnace cement and fly ash cement, and sulfate resistant cement can also be used. The particle size of the cementitious substance is usually 5 to 30μ, but if it has hydraulic properties, it is smaller than this,
Alternatively, larger ones can be used.

It is also possible to use a rapid hardening material, an expansive material, a high-strength admixture, etc., which are usually used for cement concrete as a hydraulic material. Examples of the quick-hardening material include those containing calcium aluminate as a main component, examples of the expanding material containing calcium sulfaluminate as a main component, and examples of the high-strength admixtures containing anhydrous gypsum as a main component. The particle size of these admixtures is usually
Although 0.5 to 30 μ is used, smaller or larger one can be used.

As the inorganic ultrafine powder, particles which are smaller by 1 order, preferably 2 orders than the cementitious substance, and there are no particular restrictions on the components of the ultrafine powder, but those which are readily soluble in water are not suitable. Further, the production method thereof is not particularly limited and may be an ordinary method, but from the economical aspect, pulverization,
Those produced by classification and those produced as by-products are preferred. Specifically, finely pulverized products such as blast furnace slag and fly ash, as well as siliceous dust and silica fume, which are by-products during the production of silicon, silicon-containing alloys, zirconia and the like, are suitable. In addition, calcium carbonate, silica gel, opalaceous silica, titanium oxide, aluminum oxide, zirconium oxide, various glasses, clay minerals such as bentonite and its calcined materials, amorphous aluminosilicate, chromium oxide and ultrafine powder such as activated carbon can also be used. Is.

When used as a cement admixture, these hydraulic substances are used in order to exert the effects of improving fluidity, increasing strength, improving compactness, reducing shrinkage, crack resistance, etc. 3 to 100 parts by weight of the solid content of the synthetic rubber latex.
Parts by weight are suitable.

The water reducing agent according to the present invention has an effect of improving the fluidity of a cement-kneaded product, and is a general water reducing agent or a high performance water reducing agent. As a general water reducing agent,
Oxycarboxylates, lignin sulfonates, higher polyhydric alcohols and the like can be mentioned, and as high performance water reducing agents,
Alkyl allyl sulfonate, aromatic polycyclic condensate sulfonate, salt of naphthalene sulfonic acid formalin condensate,
Examples thereof include salts of melamine sulfonic acid formaldehyde condensate, high molecular weight lignin sulfonate, and polycarboxylate. Of these, it is preferable to use the high-performance water reducing agent, but it is also possible to use them in combination. The water reducing agent is preferably used in an amount of 0.1 to 20 parts by weight or less, and more preferably 5 to 10 parts by weight, based on 100 parts by weight of synthetic resin emulgin and / or synthetic rubber latex.

The defoaming agent according to the present invention is for reducing the air content of a cement-kneaded material, and bubbles are entrained when a synthetic resin emulsion and / or synthetic rubber latex and a hydraulic substance are used in combination. To prevent the Specifically, oils and fats such as sesame oil, fatty acids such as stearic acid, alcohols such as octyl alcohol, polyesters such as sorbitan fatty acid esters and partial ester of fatty acids, ethers such as polyoxyethylene and polyoxypropylene. System, paraffin system, silicone system and the like. The amount of the defoaming agent used is preferably about 1 to 5 parts by weight based on 100 parts by weight of the solid content of the polymer latex.

As the spray drying method, the synthetic resin Emulgin and / or the synthetic rubber latex in which the water reducing agent and the defoaming agent are mixed in advance and the hydraulic substance are simultaneously applied, but the introduction routes are separately introduced into the dryer and sprayed. A three-fluid nozzle method, a two-fluid nozzle method, or a method in which a mixed slurry composed of a hydraulic substance and an emulsion is prepared in advance and the slurry is sprayed to a dryer with a two-fluid nozzle or a rotating disk can be adopted. .

[0025]

The present invention will be described in more detail with reference to the following examples.

Example 1 A synthetic resin emulsion in which a water reducing agent and an antifoaming agent were mixed in advance and a hydraulic material were simultaneously introduced into a spray dryer and dried. The spray drying method used was a three-fluid nozzle method, and the spray drying device used was a product name “Nippirosa method spray dryer of West Germany” manufactured by Nippon Dairy Machinery Co., Ltd.

Resin concentration obtained by premixing a water reducing agent and a defoaming agent while maintaining the hot air temperature at the dryer inlet at 130 ° C.
Discharge 40% by weight of synthetic resin emulsion from the center tube of the three-fluid nozzle at a rate of 3.0 to 5.0 kg / h, and water from the outer tube.
2.6 ~ 4.3kg / of hydraulic material slurry diluted to 20wt%
Discharge at a speed of h and deliver compressed air from the outermost tube to 2.0 to 3.0k
Discharged at gf / cm ² . In addition, it was also performed as a comparative example in the case where the water reducing agent or the defoaming agent was not used. As shown in Table 1, the composition powder obtained in the present invention was in a good condition.

[0028]

[Table 1] Powder state ○: Almost no blocking △: Little blocking ×: Many blocking

The materials used in Table 1 are as follows. Emulsion: Denki Kagaku Kogyo Co., Ltd. ethylene / vinyl acetate copolymer (solid content 56% by weight) Hydraulic material: Blast furnace slag, average particle size 1.0 μ by gas adsorption method Water reducing agent (a): Daiichi Kogyo Seiyaku Co., Ltd. Cell flow 110
P ", the main component is a salt of a naphthalene sulfonic acid formalin condensate (b):" Seecament FF86 / 100 "manufactured by Sika Japan, the main component is a salt of a melamine sulfonic acid formaldehyde condensate Defoamer: Toho Chemical Industry Nonion Surfactant "Pronal 502"

[0030]

According to the method of the present invention, a synthetic resin emulsion and / or a synthetic rubber latex can be made into a powder form without causing blocking, and a hydraulic polymer-containing powdery polymer composition having excellent dispersibility. You can get things. Moreover, this powdery polymer composition can be stored for a long period of time. Therefore, when the hydraulic substance-containing powdery polymer composition produced according to the present invention is used as an admixture for cement, workability is improved, and it becomes possible to obtain a solid cement hardened product having excellent durability. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobuyoshi Nakajima No. 6 Goi Minamikaigan, Ichihara City, Chiba Denki Kagaku Kogyo Co., Ltd. (72) Inventor Kazuyuki Shimoda No. 6 Goi Minamikaigan, Ichihara City, Chiba Denki Kagaku Kogyo Chiba Plant Co., Ltd. (72) Hideki Hirano 6 Goi Minami Kaigan, Ichihara City, Chiba Denki Kagaku Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A hydraulic polymer-containing powdery polymer composition comprising a synthetic resin and / or synthetic rubber, a hydraulic substance and a water reducing agent. 2. The powdery polymer composition containing a hydraulic substance according to claim 1, which further comprises an antifoaming agent. 3. A water reducing agent, or a synthetic resin emulsion and / or synthetic rubber latex in which a water reducing agent and an antifoaming agent are premixed, and a hydraulic substance are simultaneously introduced into a spray dryer and spray dried. A method for producing a powdery polymer composition containing a hydraulic substance.