JPH0710739B2 - Cement mortar composition containing epoxy resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is used in the field of civil engineering and construction for various purposes such as paving materials, flooring materials, waterproof materials, anti-food materials, adhesive materials, filling materials, repair materials, etc. The present invention relates to an epoxy resin-containing cement mortar composition.

[Prior Art] In recent years, polymer cement mortar containing a thermosetting epoxy resin as a polymer component has been widely studied for the purpose as described above (for example, JP-A-62-212251 and JP-A-6-212251).
3-156050, JP-A-63-159245, JP-A-63-182244
issue).

On the other hand, in order to improve the complicated workability of raw material mixing of the conventional epoxy resin-based polymer cement mortar, the present inventor previously described in Japanese Patent Publication No. 1-57067 (hereinafter referred to as the prior application), in which the raw material component was an epoxy resin, We proposed a composition that can simplify the work at the construction site by premixing it with an aqueous dispersion containing fine aggregates, pigments, etc. and a wettable powder mixture containing cement, an epoxy curing agent, etc. as the main components.

[Problems to be Solved by the Invention] However, the composition of the prior application is a mortar in which the aqueous dispersion, the wettable powder mixture (in the present application, a powdery curing agent), and optionally water are blended (hereinafter, blended mortar). (It is abbreviated as)) is slow to set and harden, the work process is long, and in some cases (in case of high polymer cement ratio region composition or at relatively low temperature), hydration reaction of cement is interrupted and curing failure occurs. (References: JP-A-57-77060 and JP-A-61-197458) have been desired to be improved. Further, since the composition of the prior application contains the organic solvent in the wettable powder mixture, it has a disadvantage in storage and handling of the product, and there is a problem that it can be removed.

Therefore, the present invention has the features of the prior application technology that simplifies the mixing work of the epoxy resin-based polymer cement mortar, and quickly cures after the required pot life, and additionally prevents the occurrence of cracks due to drying shrinkage. Moreover, it is an object of the present invention to provide an epoxy resin-containing cement mortar composition that can eliminate the use of an organic solvent.

[Means for Solving the Problems] The inventors of the present invention have conducted extensive experiments to solve the above problems, and as a result, in the composition of the prior application, an inorganic bond composed of Portland cement, calcium aluminates and gypsum in specific ratios. By using the material as cement,
The present invention has been found to prevent the occurrence of curing failure in a prepared mortar due to the mixing of epoxy resins.

That is, the present invention, a. Aqueous dispersion containing an epoxy resin binder, b. Portrant cement: 15-95 wt%, calcium aluminates: 1-75 wt%, gypsum: an inorganic substance consisting of 35 wt% or less Epoxy resin curing agent per 100 parts by weight of binder: 0.2 to 28 parts by weight, a powdery curing agent containing a component in which an appropriate amount of a coagulation regulator is mixed, and, if necessary, water, each of a and b The component relates to an epoxy resin-containing cement mortar composition which is adjusted in advance to a necessary amount ratio so as to promptly form a ready-to-work formulation by mixing both at the time of use.

The configuration of the present invention will be described in detail below.

The epoxy resin-containing cement mortar composition of the present invention contains an epoxy resin, an epoxy resin curing agent, Portland cement, calcium aluminates, gypsum and a setting regulator as main components.

Here, the epoxy resin is not particularly limited, and all epoxy resins can be used, but bisphenol A type liquid epoxy resin is preferable from the viewpoint of economy and versatility, and these are used as O / W type emulsions. . Further, a water-soluble or self-emulsifying epoxy resin which has undergone a special modification can also be used.

As the thermoplastic resin emulsion used in combination with the epoxy resin, for example, vinyl acetate-based, ethylene-vinyl acetate-based,
Various homo- or copolymer emulsions of ethylene-vinyl acetate-vinyl chloride, vinyl propionate-vinyl acetate, vinyl acetate-Veova, acrylic, styrene-acrylic, etc., and as rubber latex, for example, styrene-butadiene System, acrylonitrile-butadiene system,
Examples thereof include synthetic rubber latex such as urethane type. These emulsions or latexes are added for the purpose of reducing the cost of the organic binder and imparting flexibility to the cured product.

As the epoxy resin curing agent, compounds such as aliphatic polyamine-based compounds, alicyclic polyamine-based compounds, aromatic polyamine-based compounds, polyaminoamide-based compounds, and various derivatives thereof are used. The compounding amount of curing agent for epoxy resin is usually 20-
It is in the range of 100 PHR.

As Portland cement, plain Portland cement, early strength Portland cement, ultra early strength Portland cement, white Portland cement, moderate heat Portland cement, plain cement such as sulfate resistant Portland cement, or blast furnace cement, fly ash cement, silica cement. Mixed cement such as can be used.

As calcium aluminates, for example, 12CaO · 7
Al ₂ O ₃ , CaO ・ Al ₂ O ₃・ nSiO ₂ , 5CaO ・ 3Al ₂ O ₃ , 3CaO ・ Al ₂ O
₃ , 11CaO ・ 7Al ₂ O ₃・ CaF ₂ , 4CaO ・ Al ₂ O ₃・ Fe ₂ O ₃ , 3CaO ・
3Al ₂ O ₃ · crystalline or amorphous mineral _{CaF 2, 3CaO · 3Al 2 O} 3 · CaSO 4 and the like as a main component can be mentioned. In the present invention, these single or mixtures are used, and commercially available products include alumina cement, jet cement, and various quick-hardening materials.

The gypsum is not particularly limited, and anhydrous gypsum, gypsum dihydrate, gypsum hemihydrate and the like can be used alone or in combination of two or more.

The above three components constituting the inorganic binder are 15 to 95% by weight of Portland cement and 1 to 75 of calcium aluminates.
It is used in the range of wt% and gypsum 35 wt% or less, but if it deviates from this range, the action effect of preventing the curing failure of the prepared mortar is lost, or the cured product is excessively expanded and cracks occur. Cause trouble.

The mixing amount of the epoxy resin curing agent with respect to 100 parts by weight of the inorganic binder is in the range of 0.2 to 28 parts by weight, and below 0.2 parts by weight, the total amount of the epoxy resin is insufficient and the desired physical properties cannot be obtained. If it exceeds the parts, it becomes difficult to powder the mixture. The total amount of polymer per 100 parts by weight of the inorganic binder is usually in the range of 5 to 60 parts by weight.

Examples of suitable setting regulators include citric acid, gluconic acid, oxycarboxylic acids such as tartaric acid or salts thereof, lignin sulfonate, calcium hydroxide, sodium aluminate, alkali metal carbonates and other salts. Can be mentioned.

Although the amount of the coagulation regulator used is not particularly limited, it is usually 0.1 to 5 parts by weight per 100 parts by weight of the inorganic binder. 0.
If it is less than 1 part by weight, the setting will be too fast, and if it exceeds 5 parts by weight, the strength will be poor.

The present invention, in addition to the above components, if necessary, silica sand, sea sand,
Aggregates such as river sand and cold water sand, slag powder, pozzolan such as fly ash and silica fume, fiber materials such as carbon fiber, glass fiber and steel fiber, metal powder / flakes, mica, micro hollow spheres and calcium carbonate Fillers, water reducing agents such as high condensation products of naphthalene sulfonates, fluidizing agents such as melamine resin sulfonates, viscosity modifiers such as methyl cellulose and hydroxyethyl cellulose, water absorbing agents such as polyacrylates, higher fatty acid salts, zirconium Proper use of waterproofing agents such as compounds, defoaming agents, coloring agents, swelling agents, UV stabilizers, antiseptic / antifungal agents, rust preventives, antifreezing agents, foaming agents, organic solvents and any other admixtures and additives be able to.

The above-mentioned gypsum, setting control agent and each component added as necessary can be added to either or both of the aqueous dispersion (a) and the powdery curing agent (b). In addition, for aggregates and water having a large amount of miscibility, an arbitrary amount thereof may be post-added to the prepared mortar at the site of use.

The aqueous dispersion (a) in the present invention can be produced according to a method for producing a general aqueous building material, and is prepared as a slurry or a viscous liquid. The powdery curing agent (b) can be easily produced by stirring and mixing the powder component and the epoxy resin curing agent in various mixing devices. At this time, when the viscosity of the epoxy resin curing agent is high, a diluent such as a solvent or a plasticizer may be added or heated.

The preparation of the composition of the present invention is usually carried out by adding the required amount of water to the aqueous dispersion (a) and mixing the resulting mixture with the powdery curing agent (b).
And a method of adding and mixing the powdered curing agent (b) with a required amount of water and mixing the resulting mixture with the aqueous dispersion (a), and when no addition of water is required. ,
It can be carried out by a method of directly adding the powdery curing agent (b) to the aqueous dispersion (a) and mixing them.

The composition of the present invention can be applied by trowel coating, brush coating, spraying, pouring, flow spreading, etc. according to general polymer cement mortar.

[Function] In general, a polymer cement mortar containing an epoxy resin as a polymer component has a remarkably slow curing rate, and this tendency is that in the region of a relatively high polymer cement ratio, the cement is preliminarily treated with an epoxy resin curing agent like the composition of the prior application. This becomes remarkable when pre-formulation is performed by coating and forming the powdery curing agent (b), and in some cases, the hydration reaction is interrupted and curing failure may occur.

The above phenomenon is basically caused by the fact that the liquid epoxy resin infiltrates between the cement particles in the mortar, and the cement particles are covered with the resin oil film. Since it is coated with a curing agent, it is easy to form a hydrophobic resin film on the cement particle surface as the resinification reaction progresses, and water is supplied.
It is speculated that the contact is blocked and the hydration reaction is significantly hindered.

Therefore, in the present invention, this problem is solved by using an inorganic binder composed of Portland cement / calcium aluminate / gypsum in a specific ratio as the cement.

Although the mechanism for preventing hardening failure of the prepared mortar in the present invention is not clear, in the initial stage of hydration of the inorganic binder, calcium hydroxide eluted from Portland cement, calcium aluminate and gypsum undergo a hydration reaction. It is presumed that ethrine guides of fine needle-like crystals are generated as a result, and this destroys the resin film formed on the surface of the cement particles, allowing the hydration reaction of the cement to proceed smoothly. As a result, the curing failure of the prepared mortar due to the mixing of the epoxy resin in the prior application is completely prevented, and the setting of the curing time is possible by using the setting modifier. Further, the mixed powder of the inorganic binder, the epoxy resin curing agent and the coagulation regulator in a specific ratio has water dispersibility, and has an advantage that the organic solvent in the composition of the prior application can be removed.

[Examples] The present invention is described below by referring to Examples, but the present invention is not limited thereto. In addition, the part in a sentence shows a weight part.

Example 1 The compositions shown in Tables 1 and 2 were prepared using the materials listed below.

<Materials used> Epoxy resin (honorific name EP): Asahi Denka Kogyo "Adeka Resin EPES-0425" Epoxy curing agent (abbreviation EH): Fuji Kasei Kogyo "Fujicure # 5300" Ethylene vinegar emulsion (abbreviation EVA): Electric "Denka EVA Tex # 83PLE" manufactured by Kagaku Kogyo Co., Ltd. Portland cement (abbreviated as PC): Ordinary Portland cement manufactured by Nippon Cement Co., Ltd. Alumina cement (abbreviated as AC): "Alumina cement No. 1" manufactured by Denki Kagaku Co., Ltd. Jet cement (abbreviated as JC): Onoda Cement Co., Ltd. Ultra-rapid cement gypsum (abbreviation GS): Type II anhydrous gypsum, Blaine value 5,000 cm ² / g Superplasticizer (abbreviation F10): Showa Denko's "Melment F-10" viscosity modifier (abbreviation MC) : Methylcellulose antifoaming agent (abbreviation B): "Nopco 8034L" manufactured by San Nopco Coagulation regulator (abbreviation C): Mainly oxycarboxylic acid and alkali metal carbonate Mixture to be used Fly ash (abbreviation FA) Aggregate (abbreviation S): Silica sand No. 7 organic solvent (abbreviation SV): xylol Next, 38 parts of water is added to each of the powdery hardener (b) compositions shown in Table 2. To form a uniform slurry, which is added to the corresponding aqueous dispersion (a) composition shown in Table 1 to prepare a mixed mortar,
The curing time, compressive strength and crack properties were measured by the following methods. The results are shown in Table 3.

<Measurement method> Curing time: Put the sample in a 300cc beaker, and at 20 ℃,
The time at which it was not easily deformed even when a force was applied by hand using a spatula was measured and used as the curing time.

Compressive strength: Complies with JIS A 6203.

Crack: By visual inspection. Properties are ○… Good, △… Medium,
X: judged to be defective

Example 2 In the aqueous dispersion (a) -No. 1-3 formulations of Example 1,
Furthermore, 38 parts of water and 0.5 part of a water-absorbent resin were respectively mixed to prepare another composition of the present invention. This product has long-term storage stability and is compatible with powdery hardener (b) -No. 1
When used in combination with Nos. 3 to 3, it is not necessary to add water, so the powdery curing agent (b) can be directly added to the aqueous dispersion (a).
A mixed mortar can be quickly obtained by simply adding and mixing.

[Effects of the Invention] The composition of the present invention has the technical features of simplifying the raw material mixing step of the epoxy resin-containing cement mortar, and (1) is fast-curing and has good strength development, and is accompanied by the use of epoxy resin. No curing delay or curing failure occurs.

(2) The workability and the curing time can be adjusted as desired, resulting in excellent workability.

(3) Drying shrinkage is small and cracks are unlikely to occur.

(4) The organic solvent can be removed.

And so on.

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Claims (4)

[Claims] 1. An aqueous dispersion containing an epoxy resin binder, b. Portland cement 15 to 95% by weight, calcium aluminates 1 to 75% by weight, and 100 parts by weight of an inorganic binder comprising 35% by weight or less of gypsum. On the other hand, an epoxy resin curing agent 0.2 to 28 parts by weight Coagulation control agent A powdery curing agent containing an appropriate amount of a mixed component, and, if necessary, water, and the respective constituent components a and b are mixed when used. As a result, an epoxy resin-containing cement mortar composition that is adjusted in advance to a necessary amount ratio so as to quickly form a workable formulation. 2. The composition according to claim 1, wherein the epoxy resin binder comprises an aqueous dispersion of epoxy resin or a mixture of an aqueous dispersion of epoxy resin with a thermoplastic resin emulsion and / or rubber latex. 3. The composition according to claim 1, wherein a part or the whole of gypsum is contained in the aqueous dispersion (a). 4. The composition according to any one of claims 1 to 3, wherein a part or all of the setting regulator is contained in the aqueous dispersion (a).