JP4803045B2 - Urethane cement-based composition, coated flooring and its construction method - Google Patents

Description

  The present invention is excellent in blistering resistance and compression strength that there is no appearance defect due to foaming under various construction conditions, and can be cured and walked in a short time, such as a food factory, chemical factory, machine factory, etc. The present invention relates to a urethane cement-based composition suitable for industrial floors such as factory floors, coated floor materials, and a method for constructing the same.

As a conventional coating floor material and paving material, materials such as urethane resin, epoxy resin, and methyl methacrylate (MMA) have been used. However, these products are not always sufficient in heat resistance, acid resistance, alkali resistance and the like for industrial floors such as food factories and chemical factories. In addition, some of the above flooring materials include a material containing a large amount of solvent and a material that emits strong odor, and these materials are not environmentally preferable.

Therefore, a polyurethane-based cement composition composed of hydraulic cement, aggregate, water, polyol, and a compound having two or more isocyanate groups has been proposed. (See Patent Document 1) This polyurethane-based cement composition mixes the above-mentioned components in the field, thereby hydrating the water and cement, urethanizing the polyol and isocyanate, and generating carbon dioxide gas from the isocyanate and water. The accompanying ureation reaction proceeds simultaneously. When this composition is cured, it is hard and excellent in wear resistance, and in addition, has heat resistance and chemical resistance. Therefore, it can be used as a floor material excellent in durability on industrial floors such as factory floors.

Also, a dispersion (A) containing (a) an active hydrogen compound having a nitrogen atom, (b) an active hydrogen compound having no nitrogen atom, (c) water, (d) a wetting dispersant and (e) an inorganic acid And a urethane-based cement composition comprising a compound (B) having two or more isocyanate groups in the molecule and a hydraulic cement (D). (See Patent Document 2)

Although the above urethane-based cement composition has a certain pot life and good workability, it takes a lot of time to cure, so when adding a catalyst or the like to shorten the curing time, even at low temperatures There are problems of poor appearance due to foaming and low mechanical properties.
JP-A-8-169744 JP 2006-206354 A

The object of the present invention is to maintain the above-mentioned characteristics of the urethane-based cement composition, have no appearance defects due to foaming, etc. even under various construction conditions, have high compression mechanical properties, and further in an atmosphere of 5 ° C. to 40 ° C. for 5 hours. It is in a urethane cement-based composition that is hardened within and can be walked, and can be mainly used as a coating floor material or a base treatment material for a coating floor material, and provides a method for applying the coating floor material.

The inventors of the present application have disclosed oxides of metals such as calcium oxide, magnesium oxide, barium oxide, barium hydroxide, and magnesium hydroxide, which are generally used as carbon dioxide gas absorbents in order to eliminate the foaming phenomenon in particular. Although research was conducted on hydroxides and the like, it was found that none of these had a carbon dioxide absorption effect and could not be used. As a result of intensive studies on various compounds, the inventors have found specific slaked lime and have completed the present invention.
That is, the present invention relates to a slaked lime (E) produced by a heavy oil baking method in a urethane cement-based composition containing an organic polyisocyanate compound (A), water (B), a urethanization catalyst (C), and cement (D). includes, and 0.2 to 15.0 wt% der content of the total composition of the digestion lime (E) is, on the whole urethane cementitious composition, the amount of the water (B) is 1 to 10 wt%, the amount is 0.01 to 2 wt% of the urethane catalyst (C), urethane cement usage of the cement (D) is characterized by 5 to 30 wt% der Rukoto It is in providing the coating composition which consists of a composition, this composition, or the ground-treatment material for flooring, and also the construction method.

As an effect of the present invention, it has the property of being excellent in blistering resistance and high compression mechanical properties that there is no poor appearance due to foaming of the coating film under various construction conditions, and further in an atmosphere of 5 ° C. to 40 ° C. for 5 hours. The invention provides a urethane cement-based composition that can provide a material that can be hardened and walked within, a coated flooring material or a ground-treatment material for the coated flooring material, and a construction method thereof.

The present invention is further described below.
The organic polyisocyanate compound (A) used in the present invention is prepared by reacting an organic polyisocyanate compound alone or an organic polyisocyanate compound and a polyol in an ordinary manner under an excess of the organic polyisocyanate compound. is there.

  Examples of the organic polyisocyanate compound (A) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, partially carbodiimidized diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and tolylene diisocyanate. Aliphatics such as aromatic diisocyanates such as naphthalene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate Diisocyanate Over DOO, alicyclic diisocyanates such as xylylene diisocyanate, polymeric MDI, biuret of hexamethylene diisocyanate, trifunctional or more isocyanate such as trimers and the like, can be used those of one or more thereof.

Examples of the polyol include polyether polyol, polyester polyol, and polydiene polyol.
The polyether polyol is a polyol obtained by subjecting ethylene oxide, propylene oxide, butylene oxide or the like to ethylene glycol, propylene glycol, water, glycerin, trimethylolpropane, pentaerythritol or the like alone or by addition polymerization of two or more kinds.

Examples of the polyester polyol include compounds obtained by reacting a dicarboxylic acid and a dihydric alcohol by a known method. Suitable dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid, and mixtures of these acids. Examples of dihydric alcohols include ethylene glycol, propylene glycol, butanediol, hexanediol and 2,2-diethyltrimethylene glycol.

Examples of the polydiene polyol include polyisoprene polyol, polybutadiene polyol, polychloroprene polyol, and polyols hydrogenated thereto.
The polyol preferably has a number average molecular weight of 300 to 5,000.

When the organic polyisocyanate and the polyol are reacted, they are prepared by a conventional method under an excess of the organic polyisocyanate. The reaction ratio of the organic polyisocyanate and the polyol is an NCO / OH ratio of 3. It is preferably 0 or more.

As a compounding quantity of water (B), 1 to 10 weight% is a preferable range with respect to the whole urethane cement-type composition. This water (B) reacts with the organic polyisocyanate and exerts an effect on cement hydration. When the content of water (B) is less than 1% by weight, the hydration reaction of the cement tends to be insufficient, which is not preferable. When it exceeds 10% by weight, physical properties are manifested because it tends to remain as excess water. There is a tendency to become insufficient. It is also preferable to use not only water (B) but also a known polyol such as castor oil (Euric H-30), castor oil-modified polyol and plasticizer (dinonyl phthalate).

Known cements are used as the cement (D). Among these, Portland cement is preferable. Examples of 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.

As a usage-amount of cement (D), 5 to 30 weight% is preferable with respect to the whole urethane cement-type composition. If it is less than 5% by weight, foaming tends to occur, and if it exceeds 30% by weight, workability is lowered, which is not preferable.

As carbon dioxide gas absorbents in urethane cement-based compositions, calcium oxide, magnesium oxide, barium oxide, barium hydroxide, magnesium hydroxide and other metal oxides and hydroxides are generally known. Each of them had a small swelling resistance effect.
When the slaked lime (E) produced by the heavy oil baking method of the present application is used in the urethane cement-based composition as compared with the slaked lime produced by the coal baking method that is generally produced conventionally, a high swelling resistance effect is obtained. Although the detailed reason is unclear, it is estimated that slaked lime produced by the coal baking method is not caused by the addition of sodium chloride in the heavy oil baking method while sodium chloride is added during the production. ing. The slaked lime (E) produced by the heavy oil baking method is generally produced under the conditions of 1000 to 1200 ° C. using the combustion heat of heavy oil without adding sodium chloride.
The preferable average particle diameter of the slaked lime (E) in the heavy oil baking method is 1 to 20 microns or less by laser diffraction and scattering type particle size distribution analysis. If it exceeds 20 microns, the swell-resistance effect is reduced.
Moreover, even when it hardens in a short time by using slaked lime (E) manufactured with a heavy oil baking method, a high mechanical characteristic can be acquired.
The compounding quantity of the slaked lime (E) manufactured by a heavy oil baking method needs to be 0.2 to 15 weight% with respect to the whole urethane cement-type composition. Preferably it is 0.5 to 12% by weight.

When the amount is less than 0.2% by weight, the effect of absorbing carbon dioxide gas generated when the organic isocyanate compound reacts with water is less likely to foam. When the amount exceeds 15% by weight, the coating workability is significantly reduced. Therefore, it is not preferable.

The slaked lime (E) produced by the heavy oil baking method is preferably mixed with the organic polyisocyanate compound (A) and water (B) immediately before use. If it is mixed with the organic polyisocyanate compound (A) or water (B) in advance, the reaction tends to occur, the swelling resistance effect is lowered, and swelling of the coating film is likely to occur.

The urethanization catalyst (C) is a compound known to accelerate the reaction rate between an isocyanate group and an active hydrogen-containing group.
Examples of urethanization catalysts include organometallic compounds, metal salts and tertiary amines, such as dibutyltin dilaurate, zinc naphthenate, stannous octoate, stannic chloride, lead octylate, potassium oleate, Cobalt 2-ethylhexanoate, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N-ethylmorpholine, 4-dimethylaminopyridine, oxypropylated triethanolamine, β-diethylaminoethanol and N, N, Examples thereof include N ′, N′-tetrakis (2-hydroxy) ethylenediamine and a polyol using an amine as an initiator.

Among them, a polyol having an amine as an initiator and an alkylene oxide added is preferable, and a polyol compound having a number average molecular weight of 200 to 1000 is preferably used as a catalyst for obtaining appropriate workability and curability.
In order to cure within 5 hours in an atmosphere of 5 to 40 ° C. and allow walking, the blending amount of the urethanization catalyst (C) is 0.01 to 2% by weight based on the entire urethane cement-based composition. It is preferable to mix in a range.

The urethane cement-based composition of the present invention can further contain an aggregate. Aggregates include sand and low clay content gravel, crushed glass siliceous aggregates, lightweight aggregates of plastics and rubber, plastic wastes, vermiculite and the like.

These aggregates are particularly preferably used by mixing with cement. The aggregate preferably has an average particle size of 0.07 mm to 4 cm. These materials may be in the natural state or may be artificially colored, for example by using dyes, pigments or coatings.
The aggregate is preferably used in an amount of 5 to 80% by weight based on the entire urethane cement-based composition in terms of workability.

Furthermore, the urethane cement-based composition of the present invention may contain other fillers, reaction modifiers, antifoaming agents, plasticizers and the like.

  As fillers, inorganic powders such as calcium carbonate, talc and barium sulfate, and fiber materials of natural or artificial origin such as glass fiber, cotton, wool, polyethylene fiber, polyamide fiber, polyester fiber, polyacrylonitrile fiber are also used. it can. By adding talc or a fibrous material, the cement composition can be far modified, and the material that can be applied to the ramp and the standing surface can be adjusted.

  Examples of the reaction regulator include chain terminators such as monohydric alcohols and epoxy group-containing compounds. Terpineol, pure or mixed with a hydrocarbon such as pine oil, can also be used.

Examples of the antifoaming agent include known polyols such as poly (siloxane), poly (alkylsiloxane) and poly (dialkylsiloxane), and polyethylene oligomer.

  Specific examples of the plasticizer include known plasticizers such as dibutyl phthalate, dioctyl phthalate, dinonyl phthalate, butyl benzyl phthalate, tricresyl phosphate, tolyl phosphate, and tri (2-chloroethyl) phosphate. It is done.

The construction method of the present invention is produced by mixing an organic polyisocyanate compound (A) with a mixture of water (B) and a urethanization catalyst (C) at the time of construction, and cement (D) and heavy oil baking method. This is carried out by uniformly mixing a composition prepared by previously mixing slaked lime (E) with a urethane cement composition and applying it to a substrate.

In the construction method of the present invention, when mixing the various materials (A), (B), (C), (D), and (E), mixing is performed using a mixing means such as a cement mixer or a forced spatula mixer. Is preferred. Moreover, the obtained urethane cement-type composition of this invention can be used as a coated floor surface by applying to a base | substrate and making it harden | cure, for example by ironing, pouring, spraying, and another suitable method.

  Moreover, the base | substrate of this invention is constructed | assembled on the existing concrete foundation | substrate mainly for a new installation, or a repair use, and includes floor surfaces, such as a civil engineering building.

  The flooring of the present invention means a material to be applied to the floor, and includes a flooring ground treatment material and a primer as long as the material constitutes the floor.

EXAMPLES Hereinafter, although this invention is demonstrated concretely by Examples 1-2 and Comparative Examples 1-5, this invention is not limited to these Examples.

The raw material of Table 1 used for experiment is as follows.
Urethane catalyst (E) (polyol A): Polyoxyalkylene triol urethanization catalyst (E) (polyol B) obtained by ring-opening addition of propylene oxide to triethanolamine: ethylenediamine, propylene oxide and then ethylene oxide Polyoxyalkylenetriol having an oxyethylene group content of 40% by weight and a molecular weight of 500, obtained by ring-opening addition of

Euric H-30: castor oil, Ito Oil Co., Ltd. MR-100: Polymeric MDI, Nippon Polyurethane Co., Ltd. slaked lime A: Ultra fine powder slaked lime (burned with heavy oil), Tosa Lime Co., Ltd. slaked lime B: Ultra fine Powdered slaked lime (coal baked), made by Tosa Lime Co., Ltd.

<Test method>
<Compressive strength test>
Test specimens are prepared according to 8.1 of JIS-A-1181 (2005), and after curing for 1 month, they are left at room temperature for 1 day and then subjected to a compression test.
In addition, preparation of a test piece and curing conditions are performed in Example 1 and Comparative Examples 1 and 3 in a 5 ° C atmosphere, and Examples 2 and Comparative Examples 2, 4, and 5 are performed in a 40 ° C atmosphere.
<Swelling resistance test>
The material mixed in a 90 × 90 cm slate plate at 5 ° C. and 40 ° C. is applied smoothly with a trowel with a thickness of 5 mm. After curing for 2 days, the presence or absence of swelling of the coating film is visually observed. In the case where no swelling is observed, it is indicated as “◯”.
<Examination of walking time>
A material mixed in a 90 × 90 cm slate plate in an atmosphere of 5 ° C. and 40 ° C. is smoothly applied using a trowel with a thickness of 5 mm, and the time from when it is applied until it can walk on the coating film is measured. Even if it walked with athletic shoes within 5 hours, it was considered that the thing which does not show any damage on the surface was excellent in walking ability.

<Adjustment of test composition>
About Examples 1-2 and Comparative Examples 1-2 NO.2, NO.3, NO.4, NO.9 or NO.10 of Table 1 are mixed in advance with a disper and stored as agent A.
NO.5, NO.6, NO.7 or NO.8 in Table 1 is mixed in advance with a cement mixer and stored as B agent.
For the test, mix NO.1 and A agent uniformly with a cement mixer for 2 minutes. Then, B agent is thrown in, and also it mixes uniformly for 3 minutes, it is set as a test composition, and hardened | cured material is obtained.
About Comparative Examples 3-5
NO.2, NO.3, NO.4, NO.9 are mixed in advance with a disper and stored as agent A.
NO.5 and NO.6 are mixed in advance with a cement mixer and stored as B agent.
During the test, mix NO.1 and A agent uniformly with a cement mixer for 2 minutes. Then, B agent is thrown in, and also it mixes uniformly for 3 minutes, it is set as a test composition, and hardened | cured material is obtained.

The test results are shown in Table-1.

単位：重量部

Unit: parts by weight

In Example 1, no swelling of the coating film was observed in an atmosphere of 5 ° C., the walking time was within 5 hours, and the compressive strength was higher than that of the comparative example.
In Example 2, no swelling of the coating film was observed in an atmosphere of 40 ° C., the walking time was within 5 hours, and the compressive strength was higher than that of the comparative example.
In Comparative Example 1, although the walkable time was within 5 hours in a 5 ° C. atmosphere, the coating film was swollen and the compressive strength was lower than in Examples 1-2.
Although the comparative example 2 was walking time within 40 hours in 40 degreeC atmosphere, the swelling of the coating film was recognized and the compressive strength was also low compared with Examples 1-2.
In Comparative Examples 3 to 5, swelling of the coating film was observed in an atmosphere of 5 ° C. or 40 ° C., and the compressive strength was lower than that of the Examples.

Claims (5)

A urethane cement-based composition comprising an organic polyisocyanate compound (A), water (B), a urethanization catalyst (C), and cement (D), comprising slaked lime (E) produced by a heavy oil baking method, and 0.2 to 15.0 wt% der content relative to the entire composition of slaked lime (E) is, on the whole urethane cementitious composition, the water (B) amount is 1 to 10% by weight of the amount is 0.01 to 2 wt% of a urethane catalyst (C), urethane cementitious composition usage and wherein 5 to 30 wt% der Rukoto of the cement (D). The urethane cement composition according to claim 1, wherein the urethanization catalyst (C) is a polyol having an alkylene oxide added with an amine as an initiator, and a compound having a number average molecular weight of 200 to 1,000. The urethane cement-based composition according to claim 1 or 2, which is cured within 5 hours after application in an atmosphere of 5 to 40 ° C and is capable of walking. A coating floor material comprising the urethane cement-based composition according to any one of claims 1 to 3. At the time of construction, an organic polyisocyanate compound (A) is mixed with components containing water (B) and a urethanization catalyst (C), and then this mixture is mixed with cement (D) and heavy oil baking method (E Is uniformly mixed and applied to the substrate. (For the entire urethane cement-based composition, the amount of the water (B) is 1 to 10% by weight, the amount of the urethanization catalyst (C) is 0.01 to 2% by weight, and the cement (D) The amount used is 5 to 30% by weight, and the content of the slaked lime (E) is 0.2 to 15.0% by weight.)