JPH05254906A - Artificial stone composition - Google Patents

Abstract

PURPOSE:To improve surface gloss, chemical resistance, water resistance and weatherability by compounding a hydraulic inorg. material, siliceous admixture, acrylic water dispersible resin, fine aggregate and pigments at prescribed compounding ratios. CONSTITUTION:Unsatd. monomers, such as methacrylic acid, are copolymerized at 0.1 to 5wt.% to obtain the hydraulic inorg. material (e.g.: silica cement) (a). The siliceous admixture (b) which is small-grain-size fly ashes of 1 to 20mum average particle sizes is then obtd. by selection from fly ashes, etc. The acrylic water dispersible resin (c) which is superfine particle resin having 50 to 2000nm average particle sizes is obtd. by subjecting an acrylic monomer to an emulsion polymn. and adjusting the unsatd. monomer having a core and shell type differently layered structure and constituting a core part and shell part to a desired weight ratio. The fine aggregate (d), such as silica sand, and the pigments (e), such as inorg. pigments, are so disposed that the compounding ratios a/b/c/d/ e attain 10 to 50/1 to 50/1 to 30/0 to 70/0 to 50 by weight, by which the artificial stone compsn. is produced.

Description

Detailed Description of the Invention

[0001]

[Field of Industrial Application] The present invention can be used as an exterior material, a floor material, and a wall material in the field of civil engineering and construction.
The present invention relates to a stone composition having excellent water resistance and chemical resistance.

[0002]

2. Description of the Related Art It is well known that silica materials such as fly ash, blast furnace slag, and silica fume are used as an admixture for cement in order to improve various properties such as strength and water resistance of a cement-based cured product. Many proposals have been made regarding cement compositions containing such silica substances. For example, a cement composition for water-tight concrete comprising a mixture of cement / classified fly ash / silica fume / water reducing agent (JP-A-4-2642), a composite binder for concrete composed of a mixture of cement / classified fly ash / blast furnace slag (special Kaihei 4-
No. 2644), a fly ash mortar composed of a mixture of semmet / classified fly ash / fine aggregate (Japanese Patent Laid-Open No. 3-429).
No. 126652), a cement composition comprising a cement / organic fiber / classified fly ash / light weight fine aggregate mixture (JP-A-3-295843), and a cement composition comprising a cement / II type anhydrous gypsum / pozzolan substance mixture. (JP-A-3-40947).

Further, a cement-based self-leveling floor material comprising cement / lime-based expansive material / sulfonated modified resin of melamine-formaldehyde condensate (water-reducing agent) / fly ash / water-retaining agent / sand mixture (JP-A-56-84358).
Gazette), a gypsum-based composition for a casting flooring material comprising a type II anhydrous gypsum / Portland cement / fly ash mixture (JP-A-61-266340).

Also, to prevent cracking of the cement-based cured product,
A method is known in which a polymer latex is used as an additive for improving durability such as water resistance, abrasion resistance, chemical resistance, and prevention of neutralization (JP-A-53-84024). However, according to this method, although some physical properties of the cured product can be improved, the effect is insufficient in terms of water resistance suppression, neutralization suppression, etc.
A polymer latex comprising an alkyl acrylate-based copolymer fine particle having a shell-type different layer structure and a weight ratio of unsaturated monomers constituting the core part and the shell part is 90/10 to 10/90. Compounding agent for cement mortar and / or concrete as an essential component (JP-A-3-205333)
No.) or a cement mortar and / or concrete compounding agent containing an unsaturated sulfonic acid / unsaturated carboxylic acid (salt) copolymer latex as an essential component (JP-A-3-2).
57047).

Further, among the cement-based hardened materials, especially those for stone materials, there are fly ash, a melting accelerator (sodium carbonate, calcium oxide) and a hardening agent (cement),
Or mix fly ash and Portland cement,
A method of heating to 1250 to 1300 ° C. or 1400 to 1500 ° C. to obtain a fluid melt, and then gradually cooling it to form a stone material (Japanese Patent Laid-Open No. 2-116653 and No. 2-27195).
No. 7, etc.) have been proposed. Further, there has been proposed a method for reducing the weight of a fly ash molded body in which a small amount of a foaming agent (hydrogen peroxide solution) is added to fly ash and a small amount of an organic binder, and then the mixture is kneaded and molded and fired (JP-A-2-5).
9479).

However, the hardened material obtained from the above-mentioned cementitious composition has a problem that the surface is rough and thus the gloss is poor, and this point becomes important particularly in the case of stone materials.

In this regard, by adding an appropriate amount of admixture to the cement paste, thoroughly stirring and then pouring it into a mold, subjecting it to vacuum deaeration and further low temperature curing, It has been reported that hardened cement with high mechanical properties, hardened cement with a glass-like surface condition, and hardened with tile-like luster and denseness can be obtained (Kojima et al .: "Smooth glossy surface Of Cement Hardened Products with "The 45th Cement Technology Conference Proceedings 199
1, p134-137). Further, the above-mentioned JP-A-2-594.
According to Japanese Patent Publication No. 79, a glaze, glass powder or other ceramic material is attached to the surface of a molded product before firing, and the surface is made vitreous by firing, or after completion of firing, surface hardening by vitreous or ceramic by plasma spraying or the like. It is recommended to apply.

[0008]

However, in the manufacturing process of the hardened body as described above, the structure of the surface of the hardened body is not suppressed, but if possible, by the composition of the stone composition,
It is preferable to obtain a cured product having a dense surface and good gloss.

Therefore, the object of the present invention is to solve the above-mentioned problems, that is, to form a dense and smooth surface, and as a result, it is excellent in luster and has chemical resistance, water resistance and weather resistance. It is intended to provide a stone composition capable of forming a stone material having excellent properties.

[0010]

As a result of intensive studies, the present inventors have found that a stone composition having a specific composition containing an acrylic water-dispersible resin is suitable for the above purpose.
The present invention has been completed.

That is, according to the present invention, (a) a hydraulic inorganic material, (b) a siliceous admixture, (c) an acrylic water-dispersible resin, (d) a fine aggregate and (e) a pigment. Moreover, the compounding ratio is (a) / (b) / (c) / (d) / (e)
= 10 to 50/1 to 50/1 to 30/0 to 70/0 to 5
There is provided an artificial stone material composition characterized by being 0 (weight ratio).

The artificial stone material composition of the present invention is obtained by adding a water-dispersible acrylic resin in a certain amount to a composition having a specific composition containing a hydraulic inorganic material and a siliceous admixture as main components. In the inventions described in JP-A-3-205333 and JP-A-3-257047, unexpected densification of the surface of the hardened stone material was achieved, and as a result, the surface gloss was excellent and, of course, chemical resistance, water resistance and weather resistance. It becomes possible to form a hardened stone material having excellent properties.

The artificial stone material composition of the present invention will be described in detail below. The hydraulic inorganic material used in the present invention includes cements such as Portland cement, fly ash cement, silica cement, blast furnace cement, semi-water, and 2
Gypsums such as water and 6-hydrate gypsum. The amount of the hydraulic inorganic material used in the composition of the present invention is 10 to 50% by weight, preferably 20.0 to 40.0% by weight. 10% by weight
If it is less, the bending strength and the compression strength will be weak, which is not preferable as a floor material or an exterior material.

The siliceous admixture used in the present invention includes:
A known siliceous admixture that is generally used as a cement admixture is optionally used. Examples thereof include fly ash, aluminum slag, blast furnace slug, silica fume, rice husk ash, volcanic ash (natural pozzolan), and the like, among which fly ash is preferable. In this case, as fly ash, either fly ash or classified fly ash can be used, but the average particle size is improved in terms of improving the dispersibility of the hydraulic inorganic material and fly ash and smoothing the stone surface. 1-2
It is particularly preferable to use 0 μm classified fly ash. (In the case of other siliceous admixtures, the average particle size is 1 to
It is the same that the thickness of about 20 μm is preferable. )

The amount of the siliceous admixture used in the stone composition of the present invention is 1 to 50% by weight, preferably 5 to 2%.
It is 5% by weight. If it is less than 1% by weight, the effect of densifying and improving the smoothness of the surface of the obtained cured product will be reduced, while if it exceeds 50% by weight, the curing speed will be slow or the strength of the cured product will be reduced. The problem occurs.

The acrylic water-dispersible resin blended in the stone composition of the present invention can be obtained by emulsion polymerization of acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid ester. it can. In this case, the acrylic monomer includes an acrylic acid ester having an ethylenic double bond (for example, ethyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate), a methacrylic acid ester (for example, methacrylic acid). Methyl, ethyl methacrylate, butyl methacrylate, octyl methacrylate) and the like. These (meta)
The acrylates may be used alone or in combination of two or more.

Further, in order to improve the dispersibility of the hydraulic inorganic material, a copolymer of an unsaturated monomer having a carboxyl group and an ethylenic double bond in the molecule is more preferably used. As the unsaturated monomer having a carboxyl group and an ethylenic double bond in the molecule, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and their half esters, half amides or Examples thereof include salts thereof, but it is particularly preferable to copolymerize methacrylic acid in an amount of 0.1 to 5% by weight.

Further, in order to improve strength and water resistance, it is preferable to copolymerize a crosslinking agent having a plurality of functional groups in one molecule and / or a reactive unsaturated monomer. As these crosslinking agents and reactive unsaturated monomers, trimethylolpropane triacrylate, glycidyl acrylate,
Glycidyl methacrylate, bisphenol A polyoxyethylene adduct di (meth) acrylate, triallyl isocyanurate, N-methylol acrylamide, etc. may be mentioned, but 0.1 to 5% by weight relative to the unsaturated monomer.
It is preferable to use them after copolymerization.

Furthermore, monomers other than acrylic, for example, styrenes such as styrene and α-methylstyrene, within a range not impairing the performance of the acrylic water-dispersible resin of the present invention,
Dienes such as butadiene and isoprene, vinyl esters such as vinyl acetate and vinyl propionate, nitriles such as acrylonitrile and α-methylacrylonitrile, styrene sulfonic acid, α-methyl styrene sulfonic acid and salts thereof, and 2-acrylamide. 2-Methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 2-acrylamidobutane-2-sulfonic acid and salts thereof, vinylsulfonic acid and salts thereof, etc. It is possible to copolymerize the sulfonic acid type monomer and the like.
Preferred are styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid and salts thereof. The amount of these used is generally 0.1 to 40.0% by weight based on the total amount of the monomers excluding the reactive monomers.

The acrylic water-dispersible resin most preferably used in the present invention has a core-shell type different layer structure,
The weight ratio of unsaturated monomer composing the core part and the shell part is 35
/ 65 to 90/10 composed of fine polymer particles, and the weight composition of unsaturated monomer in the core part is such that the alkyl group has 1 to 8 carbon atoms 55 to 100% by weight Acrylic acid alkyl ester Alkyl group carbon Number of 1 to 4 0 to 45% by weight methacrylic acid alkyl ester Ethylenically unsaturated carboxylic acid or its salt 0 to 10% by weight Crosslinking agent 0 to 5% by weight, unsaturated monomer in shell part The weight composition of the alkyl group is 1 to 8 carbon atoms 5 to 49.9% by weight Acrylic acid alkyl ester 45 to 90% by weight of the alkyl group carbon number is 1 to 4 Methacrylic acid alkyl ester Ethylenically unsaturated carboxylic acid Or, its salt is 0.1 to 10% by weight and the crosslinking agent is 0 to 5% by weight as an essential component.

The unsaturated monomers mainly used in the core part are ethyl acrylate, butyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, particularly preferably ethyl acrylate, butyl acrylate and acrylic acid. 2-ethylhexyl is used. The unsaturated monomers mainly used in the shell part are methyl methacrylate, ethyl methacrylate, and butyl methacrylate,
Particularly preferably, methyl methacrylate is used.

Further, in order to improve the dispersibility of the cement, the core part and the shell part are more preferably copolymerized with an unsaturated monomer having a carboxyl group and an ethylenic double bond in the molecule. used. As the unsaturated monomer having a carboxyl group and an ethylenic double bond in the molecule, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and their half esters, half amides or These salts etc. are mentioned. These unsaturated monomers are preferably copolymerized in an amount of 0.1 to 5% by weight with respect to the unsaturated monomer in the core part or the shell part, but methacrylic acid is not used in the core part, It is 0.1 to the unsaturated monomer of the shell part.
It is particularly preferable to copolymerize 5% by weight.

Further, in order to improve strength and water resistance, it is preferable to copolymerize a crosslinking agent having a plurality of functional groups in one molecule in the core portion and the shell portion. As these cross-linking agents, trimethylolpropane triacrylate,
Glycidyl acrylate, glycidyl methacrylate,
Bisphenol A polyoxyethylene adduct di (meth)
Examples thereof include acrylate, triallyl isocyanurate, and N-methylol acrylamide, and trimethylolpropane triacrylate is used by copolymerizing 0.1 to 5% by weight with respect to the unsaturated monomer in the core part and / or the shell part. Preferably.

As the emulsifier for emulsion polymerization of the acrylic water-dispersible resin used in the present invention, the following anionic and nonionic emulsifiers are used.

[Representative Examples of Anionic Emulsifier] (1) Polyoxyalkylene alkylaryl ether sulfonate / sulfate salt

[Chemical 1]R₁: C₆~₂₀Alkyl group of n: 0 to 100, preferably 5 to 40 M₁Monovalent or divalent cation (2) Polyoxyalkylene alkyl ether sulphate
Salt

Embedded image R ₁ —O— (AO) n—SO ₃ M ₁ (wherein R ₁ , A, n and M ₁ are the same as above) (3) Polyoxyethylene alkylaryl ether sulfate salt

[Chemical 3] (In the formula, R ₁ , A, n and M ₁ are the same as above)

[Chemical 4] M₁, A, n: Same as above R₂: Hydrogen atom or methyl group R₃: C₁~ C₃₀Alkyl group, alkenyl group or alkyl group of
Group having phenyl group or alkenyl group, fatty acid residue

[Chemical 5] (In the formula, M ₁ , A, n, R ₂ and R ₃ are the same as above)

[Chemical 6] (Where M is₁, A, n, R₂And R₃Is the same as above)

[Chemical 7] (Where M is₁, A, n, R₂And R₃Is the same as above)

[Chemical 8] (In the formula, M₁, A, n, R₂And R₃Is the same as above m: 0,1 R_Four: -CH₂-,-CH₂CH₂-Or phenylene group)

[Chemical 9] (M ₁ , A, n, m, R ₂ , R ₃ and R ₄ are the same as above)

[Representative Examples of Nonionic Emulsifier]

Embedded image (10) Polyoxyalkylene alkyl aryl ether (In the formula, p is 0 to 100, preferably 5 to 70, and R ₂ and A are the same as above)

Embedded image (11) Polyoxyalkylene alkyl ether R ₁ —O— (AO) pH (wherein R ₁ , A and p are the same as above)

These anionic emulsifiers and nonionic emulsifiers can be used alone or in combination of two or more, but it is preferable to use one or more emulsifiers having ethylene oxide and propylene oxide groups in the molecule. More preferably, the compound of (1) above is used as the anionic emulsifier and the compound of (1) above is used as the nonionic emulsifier.
It is desirable to use one or more compounds of 0) or (11). In addition, these emulsifiers are 0.5 to the unsaturated monomer.
It is good to use in the range of -15% by weight, preferably 1-10% by weight.

As the polymerization initiator, for example, hydrogen peroxide alone or a combination of hydrogen peroxide and a carboxylic acid such as tartaric acid, citric acid and ascorbic acid, hydrogen peroxide and oxalic acid, sulfinic acid and salts or oxy of these. Combination with aldehydes, water-soluble iron salts and the like, and further peroxides such as persulfates, percarbonates and perborates, and 2,2′-azobis (2-aminodipropane) and its salts, 2, 2'-azobis (N, N'-dimethylene-isobutylamidine)
And water-soluble azo initiators such as 4,4'-azobis (4-cyanovaleric acid) and its salts can be used. For the preparation of the acrylic water-dispersible resin used in the present invention, it is preferable to use the water-soluble azo initiator described above in an amount of 0.1 to 3% by weight of the unsaturated monomer mixture.

The acrylic dispersible resin used in the present invention is
It can be prepared by the following general emulsion polymerization method using the above-mentioned unsaturated monomer, emulsifier and polymerization initiator. That is, the emulsifier is dissolved in the aqueous phase to solubilize a part of the core unsaturated monomer, a polymerization initiator is added, and then the core unsaturated monomer and the shell unsaturated monomer are added. It can be prepared by any of a monomer dropping method in which the monomer is dropped in order as it is or an emulsifier, a part of water, and a method of performing emulsion polymerization by pre-emulsion method in which an unsaturated monomer is preliminarily mixed and emulsified, but it is a drawback of emulsion polymerization. It is more preferable to use the pre-emulsification method in order to reduce the amount of the polymer deposited on a certain polymerization kettle or a stirring blade. In particular, a point to be noted when producing an acrylic water-dispersible resin having a core-shell type different layer structure is that polymerization of the core part and polymerization of the shell part are block-type bonds,
Therefore, it is preferable to perform aging for several minutes to several hours after the completion of the polymerization of the core part. The acrylic water-dispersible resin used in the present invention has a viscosity of 10 to 1000 cp (Brookfield type viscometer) at a solid content of 40% by weight, has good workability, and a low viscosity solid content. It is also possible to contain 50% or more.

The acrylic water-dispersible resin used in the present invention preferably has an average particle size of less than 2000 nm, preferably 500 nm or less, more preferably 200 nm or less. If it exceeds 2000 nm, the effect of improving the strength, water resistance and durability of the hardened stone material is often insufficient.

The acrylic water-dispersible resin used in the stone composition of the present invention can be easily obtained by emulsion polymerization as described above, but can be incorporated in the composition in the form of the obtained emulsion. The amount of the resin used in this case is 1 to 30% by weight, preferably 2 to 15% by weight, as solid content.
Is. If it is less than 1% by weight, the glossiness of the obtained cured product,
Water resistance and chemical resistance deteriorate. On the contrary, if it exceeds 30% by weight, the bending strength and the compressive strength decrease.

Further, in the present invention, it is also possible to use fine aggregate in order to increase the strength of the cured body. As the fine aggregate, sand (land sand, sea sand), silica sand, gravel, mica, natural stone powder, glass powder and the like can be used. The fine aggregate is used in an amount of 0 to 50% by weight, preferably 10 to 30% by weight. On the other hand, when it exceeds 50% by weight, the strength of the cured product is weakened.

In the present invention, it is possible to further use a pigment. As the pigment, various natural pigments, inorganic pigments and organic pigments can be used. The pigment is used in an amount of 0 to 5% by weight, preferably 5 to 20% by weight. Further, if it exceeds 50% by weight, it is disadvantageous in terms of cost.

Further, in the present invention, improvement of fluidity,
Further, in order to further improve durability, it is desirable to mix a sulfonic acid group-containing polymer and a carboxyl group-containing polymer at the time of compounding and kneading the hydraulic inorganic material and the acrylic water-dispersible resin emulsion. In this case, the polymer may be blended in the resin emulsion in advance. Examples of such a sulfonic acid group-containing polymer include lignin sulfonate, naphthalene sulfonic acid formalin condensate, sulfonated melamine resin, polystyrene sulfonate, 2-acrylamido-2-methylpropane sulfonic acid and (meth) acrylic. Examples thereof include copolymers with acids (esters). Examples of the carboxyl group-containing polymer include polyacrylic acid (salt) and copolymers of (meth) acrylic acid and (meth) acrylic acid ester. Among these, polystyrene sulfonate is particularly excellent. Examples of counter ions of these salts include alkali metals, alkaline earth metals, amines, alkanolamines and the like. Particularly preferred counterions are amines, alkanolamines, which are
It is preferable to use an equivalent ratio or higher and a triple ratio or lower with respect to the sulfonic acid. The molecular weight of this polystyrene sulfonate is preferably 3,000 to 100,000. More preferably from 5,000
It is 50,000. The content of the polystyrene sulfonate is preferably 0.01% by weight to 4.0% by weight, and more preferably 0.1% by weight to 2.0% by weight with respect to the cement. If it is less than 0.01% by weight, it is not preferable in terms of fluidity and water reducing effect (effect of reducing the amount of water to be blended),
When it exceeds 4.0% by weight, bleed-out of free water occurs, the fluidity is not improved, and further, the cured product performance such as water resistance is deteriorated, which is not preferable.

In the present invention, it is preferable to use a surfactant in order to improve the binding property between the siliceous admixture and the hydraulic inorganic material. Examples of the surfactant include alkylbenzene sulfonates (alkyl group having 12 to 1 carbon atoms).
8), alkyl (C _{12 to} C ₁₈ ) sulfate ester salt, alkylphenyl sulfate ester salt, polyoxyethylene alkylphenyl sulfate ester salt, dialkyl (C _{8 to} C ₁₄ ).
Sulfosuccinic acid ester salts, alkyl (C ₈ ~C ₁₄₎ sulfosuccinic acid monoamide, polyoxyethylene (EO:
P = 1 to 50) nonylphenyl ether, C ₁₂ -C ₁₈ fatty acid alkylol amides, polyoxyethylene (EO:
P = 1 to 50) alkyl amine, polyoxyethylene (EO: P = 2~100) alkyl diamines, fatty amides, dialkyl (C ₁₂ ~C ₁₈₎ dimethyl quaternary ammonium chloride, mono-alkyl (C ₁₂ ~C ₁₈₎ Examples include trimethyl quaternary ammonium chloride and alkylamine salts.

Further, in the present invention, conventional additives such as an air entraining agent, a water retention agent, a defoaming agent and an alkaline agent may be added. In this case, the air entraining agent includes sodium lignin sulfonate, sodium resinate, amine salt of alkylaryl sulfonate, polyoxyethylene alkylphenyl sulfate ester salt, polyoxyethylene alkyl sulfate ester salt and the like.

As the water retention agent, methyl cellulose, hydroxypropyl methyl cellulose, glyoxal-added hydroxypropyl methyl cellulose and the like are preferably used, but a water retentive component such as methyl alcohol or polyvinyl alcohol may be added. Further, a silicone-based surfactant is generally used as the defoaming agent, and slaked lime, quick lime or the like is used as the alkaline agent. Furthermore, if necessary, wood fiber, hemp fiber, PAN
Organic fibers such as fibers can be added, and a foaming agent such as hydrogen peroxide solution can also be added.

Further, in the present invention, in order to further improve the durability of the cured product containing reinforcing bars, it is effective to use a rust preventive together. Examples of rust preventives that can be used in combination include nitrites, chromates, silicates, phosphates, organic phosphates, amines, alkylphenols, mercaptans, and nitro compounds. A commercially available product obtained by using a resin emulsion and an organic phosphate-based rust preventive, and more preferably 1-hydroxyalkane-1,1-diphosphonate such as 1-hydroxyethane-1,1-diphosphonate. Compared with the nitrite, the effect of significantly improving durability can be obtained at a lower concentration.

Further, in the present invention, if necessary,
Non-ionic and anionic polymer substances, chelating agents, preservatives, pH adjusters, plasticizers, early-strength agents, slow-hardening agents, conductive (antistatic) agents, skeleton materials (earth clay) and supplementary additives You may use it as an ingredient.

The stone composition of the present invention is prepared by mixing a hydraulic inorganic material, a siliceous admixture, an acrylic water-dispersible resin emulsion, and, if necessary, fine aggregates, pigments and other optional additives with any method. It is obtained by doing.

To obtain a hardened product from the stone composition of the present invention, water is added so that the concentration of the stone composition is 15 to 60% by weight to prepare a slurry, and the resulting mixture is mixed with a suitable mold. Manufactured by pouring into and molding. In this case, as a suitable mold, for example, a width of 30 to 100
cm, a vertical width of 30 to 100 cm, and a thickness of 1 to 5 cm are used. The surface of the mold may be resin-coated with polystyrene resin, Teflon resin, polyethylene resin, polypropylene resin, nylon resin, polyester resin, acrylic resin, or the like in order to provide luster, or may be treated with glass lining or the like. May be. It is also effective to apply a release agent thinly and uniformly to the mold. In this case, examples of the releasing agent include silicone releasing agents, Teflon releasing agents, fatty acids, nonionic surfactants, anionic surfactants, cationic surfactants and the like.

In obtaining a hardened stone material, the slurry is sufficiently stirred and then poured into a mold for curing. Curing may be performed not only under normal pressure but also under pressure by attaching a lid to the mold, or under reduced pressure using a closed mold. Further, the curing may be performed at room temperature or under steam heating. The curing temperature is 5 to 100 ° C,
It is preferably in the range of 10 to 70 ° C., and preferably 5 to 180 ° C. when performed under pressure. Curing time is usually 1-2
It is in the range of 40 hours.

As a method of molding the hardened body, in addition to the method of pouring the stone composition slurry into the mold as described above, the slurry is filled in a spray gun and sprayed on a plate to be cured. There is a method of obtaining a thin plate-like cured product by a method, a method of applying a thin film with a roller, a method of coating a wall by a trowel work, a method of pouring on a floor by self-leveling property, and the like.

From the stone composition of the present invention, a hardened product having excellent surface gloss, chemical resistance, water resistance and weather resistance can be obtained. Therefore, the stone composition of the present invention is an artificial stone material, an exterior material, It is useful as a floor material, wall material, FA board, PC board, and the like.

[0045]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The parts and% shown below are based on weight.

Examples 1 to 16 According to JIS R5201, the compositions (cement, siliceous admixture, fine aggregate and pigment) shown in Tables 3 to 5 were charged in a cement mortar kneader and kneaded for 60 seconds. After that, water and the acrylic water-dispersible resin shown in Table 1 (the emulsifier used is shown in Table 2) were added, and the mixture was kneaded for 120 seconds. The mortar was poured into a resin container having a size of 56 L × 80 W × 20 Hmm to a thickness of 10 mm and cured for 3 days.

The gloss (gloss value) of the resulting cured product was measured with a SM color computer and a digital goniophotometer (manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Tables 3-5.
Shown in. The water resistance was evaluated by immersing the test piece in water for 1 week and then visually judging by a panelist. If there was no change from the initial stage, if 10 out of 10 judged <○>, 5 out of 10 turned white. If it is judged to be <×>. The acid resistance was evaluated by soaking the test piece in a sulfuric acid aqueous solution having a pH of 1 for 1 week, and then visually judging by a panelist. If no change from the initial stage was made, 10 out of 10 would judge <○>, 5 out of 10 If it is judged that the person is whitened, it is set as <x>.

The following compositions were used for each composition. Portland Cement: FUJI Cement manufactured by Mitsubishi Materials Corporation White Cement: White cement manufactured by Chichibu Cement Co., Ltd. Silica-based admixture Fly ash: Dengen fly ash manufactured by Power Development Co., Ltd. (particle size 20 to 30 μm) Aluminum slag powder : Fine powder obtained by pulverizing aluminum slag, which is a by-product of aluminum refining (particle size: 20 to 30 μm) Blast furnace slag powder: Fine powder of water granulated slag (particle size: 20- 100 μm) Rice Husquash: Rice husk ash with ultrafine particles mainly composed of SiO ₂ (particle size 10 to 100 μm) Sand: 2.5 mm under of Kashima sand in Ibaraki Prefecture Pigment: Bayerox Co., Ltd. by Bayer Japan Co., Ltd. Yellow

[0049]

[Table 1] Acrylic water-dispersible resin emulsion

[0050]

[Table 2] Emulsifier of acrylic water-dispersible resin emulsion

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

As is clear from the examples and comparative examples, the stone composition of the present invention is characterized in that the acrylic water-dispersible resin improves the dispersibility of the hydraulic inorganic material and the siliceous admixture,
Moreover, since the acrylic water-dispersible resin densely smoothes the surface of the cured product obtained from the composition of the present invention, the composition of the present invention has excellent surface gloss and, of course, chemical resistance, water resistance and weather resistance. An excellent cured product can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C04B 14:02) A 2102-4G (72) Inventor Hiroshi Morita 3-5 Takasu, Chiba, Chiba Prefecture No. 4-801

Claims (3)

[Claims] 1. A composition comprising (a) a hydraulic inorganic material, (b) a siliceous admixture, (c) an acrylic water-dispersible resin, (d) a fine aggregate and (e) a pigment, and having a compounding ratio thereof. (A) /
(B) / (c) / (d) / (e) = 10 to 50/1 to 5
The artificial stone material composition, which is 0/1 to 30/0 to 70/0 to 50 (weight ratio). 2. The average particle size of the acrylic water-dispersible resin obtained by emulsion polymerization of acrylic monomers is 50 to 2
The artificial stone material composition according to claim 1, which is an ultrafine particle resin having a size of 000 nm. 3. The siliceous admixture has an average particle diameter of 1 to 2.
The artificial stone material composition according to claim 1 or 2, which is a fly ash having a small particle size of 0 µm.