JP3561993B2 - Hardening cement composition for floor and method of hardening the same - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a hardening cement composition for floors and a method for hardening the same .
[0002]
[Prior art]
Cement-curable compositions with rapid curing capabilities that can be used for short-term (typically within a day) flooring applications are known in the art. For example, GB 1 192 864 describes a fast-setting cement-curable composition containing hydraulic cement, silica filler, water, and a polyisocyanate compound as essential components. Such compositions generally include, as another component, an active hydrogen compound. These curable cement compositions cure very quickly and, after application, cure in a fraction of the time and can provide new floors and walls.
[0003]
Such a cement-curable composition must be divided into at least two components, an active hydrogen compound component and a polyisocyanate component, until the components are mixed immediately before application. Further, in order to easily and surely perform the operation of mixing these components, it is preferable that the active hydrogen compound component in this type of cement-curable composition is stored in the form of an aqueous dispersion. However, the storage stability of the aqueous dispersion was not always good.
[0004]
To this end, JP-A-2-247214 proposes a stabilizer system comprising a polyhydroxyamine, an ethoxylated alkylphenol and a fatty acid. Although the aqueous dispersion containing the active hydrogen compound component using this stabilizer system is certainly sufficiently stable for practical use, its formulation is complicated and the polyhydroxyamine used is generally expensive. It is difficult to use industrially.
[0005]
Further, this active hydrogen compound component-containing aqueous dispersion generally provides a cement setting composition by forcibly mixing a hydrophobic polyisocyanate component and a hydrophilic hydraulic cement component at a construction site. However, this tends to result in poor mixing. Moreover if mixing is insufficient, the urethanization reaction, is part batchwise variation in urea reaction and cement hydration reaction occurs which proceeds simultaneously stretched the composition in the spreader (iron, etc., spread with it Hitoshi Las (Hereinafter the same), there is a problem in that abnormalities in performance and finished appearance (irregularity and gloss) are likely to occur.
[0006]
[Problems to be solved by the invention]
It is an object of the present invention to overcome the aforementioned problems of the prior art.
[0007]
[Means for Solving the Problems]
The present invention is the following invention which has been made to solve the above problems.
[0008]
(A) an active hydrogen-containing compound, (b) water, and (c) a first component composed of a cement water reducing agent , (d) a second component composed of hydraulic cement, (e) an isocyanate compound having two or more isocyanate groups. A hardening composition for flooring comprising at least three components of the third component consisting of (a) castor oil or hydrogenated castor oil as the active hydrogen-containing compound, and (e) having two or more isocyanate groups. Crude MDI is used as the isocyanate compound, (b) the amount of water used is (a) 5 to 300% by weight based on the active hydrogen-containing compound, and (c) the amount of cement water reducing agent is (a) the active hydrogen-containing compound. 0.1 to 5% by weight, and (d) the amount of hydraulic cement used is 10 to 500% by weight based on (a) the active hydrogen-containing compound, and (e) two or more isocyanate groups. Floor cement composition, wherein the amount of the isocyanate compound is 10 to 500% by weight with respect to (a) an active hydrogen-containing compound having.
[0009]
(A) an active hydrogen-containing compound, (b) water, and (c) a first component obtained by mixing a cement water reducing agent, (d) a second component formed of hydraulic cement , and (e) two or more isocyanate groups. A method of curing a cement-curable composition for floors, comprising mixing three components of a third component comprising an isocyanate compound having the formula: Castor oil or hydrogenated castor oil is used as the compound, crude MDI is used as (e) an isocyanate compound having two or more isocyanate groups, and (b) the amount of water used is 5 to 5 % with respect to ( a) the active hydrogen-containing compound. 300% by weight, (c) the amount of the cement water reducing agent used is 0.1 to 5% by weight based on the (a) active hydrogen-containing compound, and (d) the amount of hydraulic cement used is (a) the active hydrogen-containing compound. Against Characterized in that the amount of the isocyanate compound having two or more isocyanate groups is (e) 10 to 500% by weight based on (a) the active hydrogen-containing compound. A method for curing the curable composition.
[0010 ]
[0011]
The (c) cement water reducing agent used in the present invention is a generally referred to as a cement water reducing agent, and usually prevents the fluidity and air content of concrete, mortar or cement paste which is a hydraulic cement compound from decreasing with time. It is used to improve its workability and workability.
[0012]
Various types of cement water reducing agents are known, such as naphthalene sulfonate formaldehyde condensate-based water reducing agent, melamine sulfonate formaldehyde condensate-based water reducing agent, polycarboxylic acid-based water reducing agent, and lignin sulfonic acid-based water reducing agent. At least one cement water reducing agent selected from the group consisting of a water reducing agent, a polystyrene sulfonic acid water reducing agent, a phenol formaldehyde condensate water reducing agent, and an aniline sulfonic acid water reducing agent can be preferably used. The carboxylic acid or sulfonic acid-based water reducing agent includes those acid ester-based water reducing agents, acid salt-based water reducing agents, and the like.
[0013]
These are basically water-soluble and have the property of a surfactant having a hydrophobic portion and a hydrophilic portion in the molecule, and play a role of an emulsifier for stably dispersing a dispersion in the present invention.
[0014]
Further, when (d) a second component composed of hydraulic cement and (e) a third component composed of an isocyanate compound having two or more isocyanate groups are mixed with the dispersion, the cement water reducing agent causes the surface of the cement particles to be mixed. Coating has the effect of promoting its dispersion and improving its uniform mixing properties.
[0015]
In addition, the amount of water required to obtain appropriate fluidity is reduced, and the urethane and urea reactions accelerated by the alkali (calcium hydroxide) generated by the cement hydration reaction are suppressed, and workability is considered. Can delay the curing reaction which is too rapid.
[0016]
The (a) an active hydrogen-containing compound in the present invention, Ru with castor oil or hydrogenated castor oil.
[0017 ]
[0018 ]
[0019 ]
[0020 ]
[0021 ]
[0022 ]
[0023 ]
[0024]
The dispersion in the present invention is obtained by mixing (a) an active hydrogen-containing compound, (b) water, and (c) a cement water reducing agent. (B) the amount of water is from 5 to 300% by weight with respect to (a) an active hydrogen-containing compound.
[0025]
(C) The amount of the cement water reducing agent, 0 to (a) an active hydrogen-containing compound. 1 to 5% by weight.
[0026]
By adjusting the proportions of these, the practical storage stability of the dispersion of the present invention is sufficient, and (d) a second component composed of hydraulic cement and (e) an isocyanate having two or more isocyanate groups. The curing reaction can be delayed only by ensuring appropriate workability when mixed and cured with the third component composed of a compound.
[0027]
Further, the dispersion may contain a so-called surfactant, if necessary. The use of this surfactant can be expected to assist the dispersion stability of the dispersion and to further reduce the air that is introduced during mixing. As the surfactant that can be used, any of a synthetic surfactant, a resinate-based surfactant, and a protein-based surfactant can be used. As the type of surfactant, anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant are used alone or in combination.
[0028]
The present invention also provides (a) an active hydrogen-containing compound, (b) water, and (c) a first component comprising a cement water reducing agent, (d) a second component comprising hydraulic cement, and (e) two or more isocyanates. third component consisting of an isocyanate compound having a group, a floor cement composition comprising at least three components.
[0029]
(D) Hydraulic cement refers to a group of structural materials that harden or set when mixed with water. Portland cement and fast-setting cements characterized by a high alumina content are particularly preferred. Examples of the Portland cement include ordinary Portland cement, early-strength Portland cement, and white Portland cement which is a cement having a low iron and carbon content. Other hydraulic cements include:
[0030]
Low heat cement characterized by high content of dicalcium silicate and tetracalcium aluminoferrite and low content of tricalcium silicate and tricalcium aluminate; abnormal content of tricalcium silicate and dicalcium silicate A sulfate resistant cement characterized by a high content of tricalcium aluminate and tetracalcium aluminoferrite, an unusually low content; Portland blast characterized by a mixture of Portland cement clinker and granular slag Furnace cement; Portland cement and one or more selected from hydrated lime, granular slag, ground limestone, colloidal clay, diatomaceous earth, or other finely divided particles of silica, calcium stearate and paraffin Masonry cement, characterized by its mixture with the United States Natural cement characterized by being obtained from the sediments of Lehigh Valley; oxides of calcium in pure or impure form, with or without some clayey material Lime cement characterized by adding 5-10% of calcined gypsum to lime; volcanic ash, volcanic diatomaceous earth, pumice, limestone, santrinite or granulated slag and lime mortar A volcanic ash-mixed cement characterized by being a mixture; a calcium sulfate hydrate-based cement, characterized by containing calcined gypsum, keince cement and gypsum plaster.
[0031]
(D) the amount of hydraulic cement is 1 from 0 to 500% by weight, relative to (a) an active hydrogen-containing compound.
[0032]
(E) Examples of the isocyanate compound having two or more isocyanate groups, Ru with crude MDI.
[0033 ]
[0034 ]
[0035 ]
[0036 ]
[0037]
What is known as crude MDI is obtained by the phosgenation of a mixed polyamine prepared by reacting formaldehyde and aniline in the presence of hydrochloric acid, and comprising a isomer and a methylene-linked polyphenyl polyisocyanate containing more than two isocyanate groups. ing than intermingled matching is diphenylmethane-4,4'-diisocyanate.
[0038 ]
[0039]
(E) the amount of the isocyanate compound having two or more isocyanate groups is 1 from 0 to 500% by weight, relative to (a) an active hydrogen-containing compound in the dispersion.
[0040]
The cement composition in the present invention may contain a filler, a reaction modifier, an antifoaming agent, a plasticizer, a curing accelerator, a conductivity-imparting agent, and bitumen.
[0041]
As the filler, a siliceous filler is preferred. Examples of the siliceous filler include sand and gravel having a low clay content, ground glass, and the like, and those having a washed particle size of 0.076 mm to 4 cm are desirable. These materials may be in their natural state or artificially colored, for example, by the use of dyes or pigments.
[0042]
In addition to the siliceous fillers, fillers such as pulverized plastics can also be used. Examples of the plastic pulverized material include colorless or colored plastic pulverized chips, turnings, or granules. Plastic waste from trimming injection molded or otherwise molded articles can also be used.
[0043]
Suitable plastic materials are thermoplastic or thermoset polymers and copolymers. For example, nylon polymers, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, urea / formaldehyde polymers, phenol / formaldehyde polymers, melamine / formaldehyde polymers, acetal polymers and copolymers, acrylic acid polymers and copolymers, acrylonitrile / butadiene / styrene terpolymers, Examples include cellulose acetate, acetate, polycarbonate, polyethylene terephthalate, polystyrene, polyurethane, polyethylene and polypropylene.
[0044]
In addition, sawdust, wood chips, pumice stone, vermiculite, and fibrous materials of natural or artificial origin, such as glass fiber, cotton, wool, polyamide fiber, polyester fiber, and polyacrylonitrile fiber can be used.
[0045]
It is particularly preferable to use the filler in a mixture with the hydraulic cement.
[0046]
Examples of the reaction modifier include a chain terminator such as a monohydric alcohol, a monocarboxylic acid, or an epoxy group-containing compound. Terpineol, either pure or mixed with a hydrocarbon such as, for example, pine oil, can also be used.
[0047]
Examples of the monohydric alcohol include saturated alcohols such as methanol, hexanol, isooctanol, nonanol, decanol, dodecanol and cetyl alcohol, unsaturated alcohols such as allyl alcohol and propargyl alcohol, and alkylene oxide adducts thereof. No.
[0048]
Monocarboxylic acids include formic acid, acetic acid, eleostearic acid, linolenic acid, linoleic acid, oleic acid, stearic acid and the like.
[0049]
As the epoxy group-containing compound, a mixed fatty acid obtained by oxidizing a fat or oil such as soybean oil or castor oil is first esterified with a monohydric alcohol, diol or polyfunctional polyol, and then the obtained mixed ester is epoxidized. Epoxidized oils and fats, bisepoxy compounds derived from diphenylolpropane and epichlorohydrin, and compounds containing at least one epoxycyclohexane group or epoxycyclopentane group.
[0050]
In the cement composition of the present invention, the isocyanate component and water coexist in the cement composition, but a sufficient amount of hydraulic cement is present, and carbon dioxide generated when the isocyanate component reacts with water is removed. Foaming is unlikely to occur because it is sufficiently basic to absorb. However, if the cement composition has a tendency to foam upon curing, an antifoaming agent can be used.
[0051]
Specifically, calcium oxide, magnesium oxide, barium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, cadmium hydroxide, calcium silicate, barium silicate, sodium silicate, Metal oxides, hydroxides, basic salts, complex salts, double salts, and the like, such as lead hydroxide and basic lead acetate, are preferred. In addition, poly (siloxane), poly (alkylsiloxane), poly (dialkylsiloxane) and the like can also be used.
[0052]
Specific examples of the plasticizer include plasticizers such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, butylbenzyl phthalate, tricresyl phosphate, tritolyl phosphate, and tri (2-chloroethyl) phosphate, and chlorinated acid. Hydrocarbons.
[0053]
Curing accelerators are compounds known to accelerate the reaction rate between isocyanate groups and active hydrogen containing groups. Suitable promoters include, for example, organometallic compounds, metal salts and tertiary amines, such as dibutyltin dilaurate, tetrabutyl titanate, zinc octoate, zinc naphthenate, stannous octoate, stannic chloride. , Ferric chloride, lead octoate, potassium oleate, cobalt 2-ethylhexanoate, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, 1,4-diazabicyclo [2. 2.2] octane, 4-dimethylaminopyridine, oxypropylated triethanolamine, β-diethylaminoethanol and N, N, N ′, N′-tetrakis (2-hydroxy) ethylenediamine.
[0054]
Further, ferrite can be used for the purpose of imparting conductivity. Ferrite refers to an iron oxide having a composition represented by MO.Fe ₂ O ₃ . Here, M is a metal such as manganese, iron, cobalt, nickel, copper, and zinc. This ferrite is blended as a powder, but the size of the powder is not particularly limited, and usually, a powder having a size of 10 to 500 μm, preferably 50 to 200 μm is used. The mixing ratio of ferrite is not limited, but is usually in the range of 10 to 100% by weight based on the cement composition.
[0055]
Bitumen (which is a distillation residue of crude oil, which has an aliphatic nature in nature and has substantially no reactivity with isocyanate) may be used. This generally improves flexibility and water resistance. Coal tar pitch may also be added to the composition.
[0056]
The present invention further provides a first component obtained by mixing (a) an active hydrogen-containing compound, (b) water, and (c) a cement water reducing agent, (d) a second component comprising hydraulic cement, and (e) A method for curing a cement curable composition for floors , comprising mixing three components of a third component comprising an isocyanate compound having two or more isocyanate groups, and then applying and curing the composition on a substrate.
[0057]
In the present invention, when mixing various materials, or when mixing three components of the first component, the second component and the third component, a method of mixing using means such as a cement mixer or a forced spatula mixer is used. preferable. The cement composition can also be applied to the substrate and cured, for example, by troweling, pouring, spraying, or any other suitable method.
[0058]
【Example】
(Example 1)
70 parts of castor oil (manufactured by Ito Oil Co .; Euric H-30), 1.5 parts (parts by weight, the same applies hereinafter) of a high-performance AE water reducing agent (manufactured by Kao Corporation; naphthalene sulfonate formaldehyde condensate-based water reducing agent) And Mighty 2000R) were stirred and mixed in 27.5 parts of water to prepare a castor oil dispersion. This dispersion exhibited favorable storage stability, high and low temperature stability.
[0059]
To 100 parts of this dispersion, 100 parts of crude MDI (manufactured by Nippon Polyurethane Industry Co., Ltd .; MR100) was mixed, and 150 parts of ordinary Portland cement and 350 parts of sand (JIS silica sand No. 3/4/6/6 = 1 /) (1/1 weight ratio) and mixed until a uniform composition was obtained.
[0060]
When this composition was applied to a substrate and applied to form a floor, it was easy to spread (stretched with a trowel, spread and evened out). The floor was able to walk on the floor within 24 hours after construction.
[0061]
(Example 2)
42 parts of castor oil (Euric H-30), 30 parts of butylbenzyl phthalate, 1.4 parts of a high-performance AE water reducing agent (Mighty 2000R), and 0.5 parts of a polysiloxane-based defoamer ( Shin-Etsu Chemical Co., Ltd .; KM89) was stirred and mixed in 25.6 parts of water to prepare a castor oil dispersion. This dispersion exhibited favorable storage stability, high and low temperature stability.
[0062]
To 100 parts of this dispersion, 100 parts of crude MDI (manufactured by Nippon Polyurethane Industry Co., Ltd .; MR350) was mixed, and 135 parts of white cement (manufactured by Nippon Cement Co., Ltd.), 350 parts of sand (the above-mentioned silica sand No. 4), and 15 parts Of chromium oxide pigment (manufactured by Bayer AG; GN) were added and mixed until a uniform composition was obtained.
[0063]
When the obtained composition was applied to a base and spread to form a floor, the spread was easy. The floor surface was able to walk within 24 hours after construction, and showed a uniform and good finished appearance without unevenness.
[0064]
(Comparative Examples 1-2)
When a dispersion was prepared in the same manner as in Example 1 or Example 2 except that the high-performance AE water reducing agent (Mighty 2000R) was not blended, separation immediately occurred. Further, when a composition was prepared in the same manner using this dispersion, a sharp increase in viscosity started immediately after mixing, and sufficient fluidity was not obtained. There were noticeable blisters and pinholes.
[0065]
【The invention's effect】
The dispersion for mixing a cement composition in the present invention has very good storage stability. In addition, the dispersion has good mixing properties when mixed with a component composed of hydraulic cement and a polyisocyanate compound. Further, the cement composition obtained by mixing them is easy to apply.

Claims (4)

(A) an active hydrogen-containing compound, (b) water, and (c) a first component composed of a cement water reducing agent, (d) a second component composed of hydraulic cement, (e) an isocyanate compound having two or more isocyanate groups. A floor cement hardening composition consisting of at least three components of a third component consisting of :
(A) using castor oil or hydrogenated castor oil as the active hydrogen-containing compound; (e) using crude MDI as an isocyanate compound having two or more isocyanate groups,
(B) The amount of water used is 5 to 300% by weight with respect to (a) the active hydrogen-containing compound, and the amount of (c) the cement water reducing agent is 0.1 to 5% by weight with respect to (a) the active hydrogen containing compound. %, (D) the amount of hydraulic cement used is (a) 10 to 500% by weight based on the active hydrogen-containing compound, and (e) the amount of isocyanate compound having two or more isocyanate groups is (a) active. A hardening cement composition for floors, which is 10 to 500% by weight based on the hydrogen-containing compound . (C) The cement water reducing agent is a naphthalene sulfonate formaldehyde condensate water reducing agent, a melamine sulfonate formaldehyde condensate water reducing agent, a polycarboxylic acid water reducing agent, a lignin sulfonic acid water reducing agent, a polystyrene sulfonic acid water reducing agent. The cement hardening composition for floors according to claim 1, which is at least one kind of cement water reducing agent selected from the group consisting of a phenol formaldehyde condensate water reducing agent and an aniline sulfonic acid water reducing agent. (A) an active hydrogen-containing compound, (b) water, and (c) a first component obtained by mixing a cement water reducing agent, (d) a second component formed of hydraulic cement, and (e) two or more isocyanate groups. mixing a third component comprising an isocyanate compound, the three components of which has a, then a curing technique for the floor cement curable composition characterized thereby applied and cured to a substrate,
(A) using castor oil or hydrogenated castor oil as the active hydrogen-containing compound; (e) using crude MDI as an isocyanate compound having two or more isocyanate groups,
(B) The amount of water used is 5 to 300% by weight with respect to (a) the active hydrogen-containing compound, and the amount of (c) the cement water reducing agent is 0.1 to 5% by weight with respect to (a) the active hydrogen containing compound. %, (D) the amount of hydraulic cement used is (a) 10 to 500% by weight based on the active hydrogen-containing compound, and (e) the amount of isocyanate compound having two or more isocyanate groups is (a) active. A method for curing a hardening cement composition for floors, comprising 10 to 500% by weight based on a hydrogen-containing compound . (C) The cement water reducing agent is a naphthalene sulfonate formaldehyde condensate water reducing agent, a melamine sulfonate formaldehyde condensate water reducing agent, a polycarboxylic acid water reducing agent, a lignin sulfonic acid water reducing agent, a polystyrene sulfonic acid water reducing agent. 4. The method for curing a cement curable composition for floors according to claim 3, which is at least one type of cement water reducing agent selected from the group consisting of a phenol formaldehyde condensate-based water reducing agent and an anilinesulfonic acid-based water reducing agent.