JP2670625B2 - Compounding agent for hydraulic inorganic materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to a compounding agent for hydraulic inorganic materials, which comprises an aqueous emulsion and a polymer having a sulfonic acid group as essential components.

(Prior art)

In recent years, hydraulic inorganic materials such as cent paste, mortar, concrete, grood, and plaster have been used in civil engineering, construction,
Used in large quantities in secondary concrete products and other fields. For these hydraulic inorganic materials, their adhesive strength, waterproofness, chemical resistance, bending strength, mechanical strength such as tensile strength,
Alternatively, many proposals have been made to improve the abrasion resistance and durability, and to add various compounding agents in order to improve the appearance of these structures or molded articles to increase added value.

For example, JP-A-60-1003061, JP-A-60-251160,
JP-A-60-173044, JP-A-57-67061, JP-A-57-7
No. 7059, JP-A-59-102480, JP-A-58-49653 and the like describe styrene / vinyl chloride / ethylene terpolymer emulsion, ethylene for a hydraulic inorganic composition such as mortar and cement. It is disclosed that a combination of a vinyl acetate copolymer emulsion, a styrene-butadiene synthetic rubber latex and a polymer dispersion of a combination thereof, and various polymer compound compounding agents such as a composite polymer emulsion are added.

In these conventional methods, although the physical properties and appearance of the hydraulic inorganic composition described above can be improved for some time, these performances have not yet been sufficiently satisfied.

Therefore, the present inventors, as a method of solving these problems, first to the hydraulic inorganic material, the average particle diameter is 300nm
The method of blending an aqueous emulsion having a crosslinked structure was proposed below (Japanese Patent Application Nos. 62-323275 and 62-305367).
issue). However, according to the subsequent studies, in these methods, the aqueous emulsion used is a polymer latex of ultrafine particles, and thus is highly thixotropic,
Therefore, it was found that a large amount of lumps (aggregates) may be formed when the hydraulic inorganic material and the aqueous emulsion are kneaded. When the weight ratio of water / cement is increased to suppress lumps and the fluidity is improved, a new problem arises that the strength of the cured product is insufficient or the durability is poor.

〔Purpose〕

The object of the present invention is to improve fluidity when kneading a hydraulic inorganic material, a compounding agent and water, unlike the above-mentioned conventional compounding agents, and further, a hydraulic inorganic material cured product (hereinafter abbreviated as a cured product). It is an object of the present invention to provide a hydraulic inorganic material compounding agent which can enhance the aesthetic appearance and further improve various properties such as water resistance, solvent resistance and durability.

〔Constitution〕

The compounding agent for hydraulic inorganic material of the present invention is characterized by comprising (a) an aqueous emulsion having an average particle size of 300 nm or less and having a crosslinked structure, and (b) a polystyrene sulfonate as essential components.

The aqueous emulsion, which is the first component of the compounding agent for hydraulic inorganic material of the present invention, has as a first component an aqueous emulsion whose average particle size is 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less. Is a requirement.

Aqueous emulsions are essentially formed by filling and fusing particles, so that the average particle size is required to be small.In the present invention, the average particle size is 300 nm or less as described above. Since it is limited to preferably 200 nm or less, more preferably 100 nm or less, the impregnating property or kneading property to a hydraulic inorganic material is also good, and heat fusion, smoothness of the film and the surface of the inorganic cured body, glossiness, etc. It is possible to greatly improve various performances of.

When the average particle diameter exceeds 300 nm, the fusion property (denseness) when forming a film (inorganic cured body) is poor, and the hydraulic inorganic cured body may contain a large amount of free water. Further, the kneadability with the hydraulic inorganic material is poor, and the bleed out of the aqueous emulsion may occur, so that the glossiness and smoothness of the film and the surface of the inorganic cured material may be lacking. Can not be achieved.

The second characteristic of the aqueous emulsion to be cut according to the present invention is that it has a crosslinked structure in the particles and / or in the particles of the aqueous emulsion.

That is, in the aqueous emulsion of the present invention, the functional groups of the raw material unsaturated monomer, or the functional groups of the emulsifier are ion-bonded, hydrogen-bonded, or condensed within the particles and / or between the particles. It is presumed that it forms a film (cured product) having excellent transparency, tackiness, water resistance and mechanical strength because it is crosslinked by a polymerization reaction or the like.

In addition, the average molecular weight of the crosslinked aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic material of the present invention, is generally hundreds of thousands or more, and most is about several million to several tens of millions,
Further, those having a high degree of cross-linking may exhibit tens of millions to about one billion, and in some cases exhibit a high molecular weight.

 Hereinafter, the present invention will be described in more detail.

The aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic materials of the present invention, can be easily obtained by emulsion polymerization of unsaturated monomers.

As the unsaturated monomer, (meth) acrylic esters represented by the following general formula (I) (Wherein R ₁ and R ₂ are hydrogen or a methyl group, and R ₃ is an alkyl group having 1 to 18 carbon atoms), as well as vinyl acetate, vinyl propionate, vinyl butyrate and other lower fatty acid vinyl esters, acrylonitrile,
Nitriles such as methacrylonitrile, styrene, α-
Styrenes such as methyl styrene and chlorostyrene, vinyls such as vinyl chloride and vinyl bromide, vinylidene chloride such as vinylidene chloride and vinylidene bromide, alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, butadiene, chloroprene, Dienes such as isoprene and vinyl pyridine are exemplified, and (meth) acrylates,
The use of lower fatty acid vinyl esters, nitriles and styrenes is preferred.

In the present invention, the unsaturated monomer to be copolymerized with the unsaturated monomer is used to further strengthen the crosslinked structure in the particles of the aqueous emulsion to be formed and / or between the particles, and to form a film. Sometimes unsaturated monomers having a reactive functional group are preferably used to promote crosslinking, but even unsaturated monomers having no reactive functional group may be used.
In the emulsion polymerization system, it is also possible to use an unsaturated monomer which can be converted into a compound having active hydrogen.

Examples of the unsaturated monomer having such a reactive functional group include compounds represented by the following general formulas (II)-(VIII). These monomers can be used alone or in combination of two or more kinds, and if necessary, other copolymerizable unsaturated monomers can be used in combination.

(Where R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , A, B, D, E, t ₁ , t ₂ and t
₃ is as follows.

R ₁ , R ₂ , a hydrogen atom or a methyl group R ₄ ; an alkylene group having 2 to ₄ carbon atoms R ₅ ; a direct bond, an alkylene group having 1 to 3 carbon atoms, a phenylene group or a substituted phenylene group R ₆ ; an oxygen atom or -NH- R _7; hydrogen, alkylol group or 1-5 C1-5 alkyl group having a carbon R _9;; hydrogen, alkylol groups R ₈ of C1-5 alkylene of 1 to 4 carbon atoms group a; methylene group or a carbonyl group B; -CH ₂ O- or a carboxyl group D; hydrogen atom, an alkyl group having 1 to 3 carbon atoms, carboxyl group, Or -CONHCONH ₂ E; a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -CH ₂ COO
H t ₁ ; real number of 0 to 20 t ₂ ; integer of 0 or 1 t ₃ ; integer of 0 to 10) General formulas (II), (III), (IV), (V), (VI),
Examples of specific compounds of (VII) and (VIII) include:
The following can be mentioned.

Examples of General Formula (II) Chrysidyl Acrylate Glycidyl Methacrylate Chrysidyl Crotonate Glycidyl Allyl Ether Examples of General Formula (III) Hydroxyethyl Acrylate Hydroxyethyl Methacrylate Hydroxyethyl Crotonate Hydroxypropyl Acrylate Hydroxypropyl Methacrylate Hydroxypropyl Crotonate Hydroxybutyl Acrylate Hydroxy Sibutyl methacrylate Polyoxyethylene monoacrylate Polyoxyethylene monomethacrylate Polyoxyethylene monotonate Polyoxypropylene monoacrylate Polyoxypropylene monomethacrylate Polyoxypropylene monotonate Polyoxybutylene monoacrylate Polyoxybutylene monotonate Hydroxy Ethyl allyl ether hydroxypropyl allyl ether hydroxybutyl allyl ether polyoxyethylene allyl ether polyoxypropylene allyl ether polyoxybutylene allyl ether Examples of general formula (IV) allylamine acrylamine methacrylamine aminostyrene α-methylaminostyrene general formula (V ) Examples Acrylamide Methacrylamide Aminopropylmethacrylamide Monomethylacrylamide Monoethylacrylamide Diethylolaminopropylacrylamide Example of the general formula (VI) Acrylic acid Methacrylic acid Crotonic acid Itaconic acid Maleic acid and its monoester of alkyl group having 1 to 5 carbon atoms Or anhydride fumaric acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms Nido Alanide fumaric acid N-carbamoylmaleamide N-carbamoylfumaric amide Example of general formula (VII) Methylallylthiol methylmercaptostyrene Example of general formula (VIII) N-methylolacrylamide N-methylolmethacrylamide N- Methylol crotonic acid amide N- (2-hydroxyethyl) acrylic acid amide N- (2-hydroxyethyl) methacrylic acid amide N- (2-hydroxypropyl) acrylic acid amide N- (2-hydroxypropyl) methacrylic acid amide The ratio of the saturated monomer and the unsaturated monomer having a reactive functional group to be used is 99/1 to 60/40 (weight), preferably 99/1 to 90/10 (weight). This usage rate is 99/1
If it is larger, the degree of cross-linking within and between particles of the resulting aqueous emulsion will be smaller, and if it is smaller than 60/40, the emulsion copolymerization will lack and a large amount of aggregates will be formed or the film-forming property will be poor. The film may be cracked or streaked.

The emulsifier used when emulsion-polymerizing the aqueous emulsion, which is the first essential component of the hydraulic inorganic material compounding agent of the present invention, using the above-mentioned unsaturated monomer, has an average particle diameter as described above. At 300 nm or less, any emulsifier can be used as long as it is an emulsifier that forms an aqueous emulsion having a crosslinked structure, but as a particularly preferred emulsifier,
The following general formulas (IX), (X), (XI), (XII), (XII
I) and (XIV) and the like, at least one reactive emulsifier, a sulfonate emulsifier represented by the general formula (XV), and a polyoxyalkylene ethylenically unsaturated carboxylic acid polyester represented by the general formula (XVI) ( Hereinafter, it is necessary to use an anionic emulsifier consisting of at least three components of poly (meth) acryloyl type emulsifier.

(Wherein, R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , a ₁ ,
a ₂ , a ₃ , a ₄ , M, m and G are as follows.

R ₁₀ ; an alkylene group having 2 to 4 carbon atoms R ₁₁ ; a hydrocarbon group which may have a substituent, a phenyl group, an amino group or a carboxylic acid group R ₁₂ , R ₁₆ ; a hydrogen or methyl group R ₁₃ ; a substituent May be a hydrocarbon group R ₁₄ , R ₁₅ ; hydrogen or an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, and preferably one of R ₁₄ or R ₁₅ A ₁ , a ₂ , a ₃ , a ₄ ; the average number of moles of addition a ₁ , a ₂ , a ₃ ; 0 to 50 real numbers a ₄ ; 1 to 50 The number of moles of alkylene oxide added in the molecule, which is a real number, is preferably 8 or more M; a monovalent or divalent cation, and preferably an amine (salt).
Particularly preferably, the alkanol number of trialkanolamine salt m; M _{-O-C n H 2n -g z} (R 18) g 2 -O- R 16, R 17; hydrogen or carbon atoms 1-2 alkyl group R _18; hydrogen or Or g ₁ ; an integer of 0 to 5 g ₂ ; an integer of 0 to 10 n; an integer of 1 to 10 a ₅ ; a real number of 1 to 50 And y: a real number of 1 to 5 R ₁₃ , R ₂₀ ; hydrogen or an alkyl group having 1 to 20 carbon atoms Y ′; an alkylene group having 3 to 8 carbon atoms, an oxygen or a carbonyl group). Ultrafine particles with a fine cross-linking structure inside and / or between particles, and further, with zeta potential of -30 mv or less, coalescence of particles and suppression of aggregation for a long period of time Dispersion stability In order to obtain a fine particle pre-crosslinked aqueous emulsion which is also excellent in (a) as an emulsifier used in emulsion polymerization of the unsaturated monomer, (a) the general formula (IX), (X), (XI), (XII), At least one reactive emulsifier represented by (XIII) or (XIV); (b) a sulfonate-type emulsifier represented by the general formula (XV); and (c) a poly (c) represented by the general formula (XVI). (A) / (c) ) = 9/1 to 1/9 weight ratio, preferably 4/1
˜1 / 4 weight ratio, (b) / (a) + (c) = 7/3 to 1/9 weight ratio, preferably 3/2 to 1/4 weight ratio.

If the usage ratio of (a) / (c) is larger than 9/1,
When the crosslinkability and (or dispersion stability) of the resulting aqueous emulsion deteriorates, and if it is less than 1/9, a large amount of aggregates will be generated during emulsion polymerization, or the average particle size of the resulting aqueous emulsion will increase. There is.

When the ratio of (b) / (a) + (c) used is greater than 7/3, the degree of cross-linking inside and / or between particles of the resulting water emulsion becomes small, resulting in a transparent film. Poor water resistance and solvent resistance, lack of microemulsification or solubilization of unsaturated monomers when less than 1/9, the average particle size of the resulting aqueous emulsion becomes large, or the particles become particles with each other as the emulsion polymerization progresses. Even if coalesce and aggregate to become cloudy, or even if an aqueous emulsion of transparent or translucent fine particles is generated, the zeta potential is negatively small, and coalescence and aggregation of particles will occur if they are left to stand for a long period of time. It easily occurs, coarse particles are formed, and it becomes remarkably cloudy, and the aqueous emulsion causes layer separation, or the viscosity is remarkably increased.

When these emulsifiers are used in the above ratio, they are ultrafine particles, have a crosslinked structure, have a high negative zeta potential, and are dispersed over a long period of time to suppress coalescence and aggregation of particles. It is possible to produce an aqueous emulsion having excellent properties and also exhibiting a glass transition temperature higher than the value calculated by the weight fraction method.

The amount of the emulsifier used is suitably about 0.1 to 15% by weight, and preferably 0.5 to 10% by weight, based on the unsaturated monomer to be subjected to emulsion polymerization.

In addition, known anionic, nonionic and cationic surfactants may be added as necessary. Specific examples thereof include higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, and styrenated phenol alkylene oxide. Adducts and their sulfate types, olefin sulfonate types such as α-olefins, long-chain alkylamine alkylene oxide adducts and quaternary ammonium salt types of long-chain alkylamine alkylene adducts, N- (1,2- Dicarboxyethyl) -N
-Sodium salt of octadecyl sulfonic acid monoamide,
Dialkyl sulfosuccinate, bleached ceramic resin,
Examples are 4-hydroxy-4,5-dicarboxylic bentadecanoic acid or 4,5-dicarboxy-pentadecanoloid organic and inorganic salts.

In particular, when an aggregate (dama) is formed in a compound such as a hydraulic inorganic material (cement, gypsum, etc.) and the aqueous emulsion of the present invention, the above polyoxyethylene (polyoxypropylene) (di) alkylphenyl is used. When nonionic surfactants such as ether, polyoxyethylene (polyoxypropylene) alkyl ether, and polyoxypropylene ethylene glycol are blended with the above emulsified compositions (a), (b) and (c), it is effective in suppressing lumps. Is.

Then, in obtaining the aqueous emulsion which is the first essential component of the compounding agent for hydraulic inorganic material of the present invention, the conventionally known emulsion polymerization method is used as it is in the presence of the unsaturated monomer and the emulsifier. Can be used. For example, in the presence of a polymerization initiator corresponding to 0.1 to 5% by weight of an unsaturated monomer, a polymer of an unsaturated simple substance is emulsified and dispersed in water at a concentration of 10 to 60% by weight to perform emulsion polymerization. Good.

As the polymerization initiator, a water-soluble single initiator or a water-soluble redox initiator used in ordinary emulsion polymerization is used, and as such, for example, hydrogen peroxide alone or hydrogen peroxide and tartaric acid, citric acid, In addition to combinations with carboxylic acids such as ascorbic acid, hydrogen peroxide and oxalic acid, sulfinic acid and salts thereof or oxyaldehydes, water-soluble iron salts, etc., sulphates, percarbonates, and persulfates. Peroxides such as borates and 2,2′-azobis (2-amidinopropane) and its salts, 2,2′-azobis (N, N-dimethylene-isobutylamidine) and its salts,
Water-soluble azo initiators such as 4,4'-azobis (4-cyanovaleric acid) and salts thereof can be used.

In particular, when the water-soluble azo initiator is used, it is easy to prepare an aqueous emulsion which is the first essential component of the hydraulic inorganic material compounding agent of the present invention.

The second component of the hydraulic inorganic material compounding agent of the present invention is polystyrene sulfonate.

Examples of the counter ion of these salts include alkali metals, alkaline earth metals, amines, alkanolamines and the like. Particularly preferred are amines and alkanolamines, and specifically, alkylmonoamines having 1 to 5 carbon atoms, respective alkyldiamines having 1 to 5 carbon atoms, alkyltriamines, and monoalkanolamines having 2 to 12 carbon atoms, Examples thereof include dialkanolamines and trialkanolamines having 2 to 5 carbon atoms. From the viewpoint of preventing acidification of the hydraulic inorganic material, it is preferable to use the alkaline substance which generates these counterions in an amount of 1 equivalent or more and 3 equivalents or less with respect to the sulfonic acid group.

As the polystyrene sulfonate used in the present invention, a monomeric pair of styrene sulfonate is homopolymerized by a known method or copolymerized with a copolymerizable ethylenically unsaturated carboxylic acid or an anhydride thereof. A homopolymer or a copolymer of polystyrene sulfonate obtained by the above process can be used. Further, polystyrene or an alkyl group having a carbon chain length of 2 to 12 obtained by reacting polystyrene with an olefin or alcohol having 2 to 12 carbon atoms in the presence of a catalyst such as activated clay, sulfuric acid, etc. Alkylated partially alkylated polystyrene, or a copolymer of styrene obtained by copolymerization with an ethylenically unsaturated carboxylic acid copolymerizable with styrene or an anhydride thereof, a sulfuric acid by a known method, anhydrous A polystyrene sulfonate obtained by directly sulfonation using a sulfonating agent such as sulfuric acid or fuming sulfuric acid, and then filtering out and neutralizing unreacted polystyrene, partially alkylated polystyrene or styrene copolymer. May be.

The molecular weight of the polystyrene sulfonate is not particularly limited, but is preferably in the range of 5,000 to 100,000 in terms of weight average molecular weight.

The sulfonation rate of the polystyrene sulfonate obtained by sulfonation of polystyrene or the like is preferably 70% or more from the viewpoint of improving fluidity. If it is less than 70%, the fluidity will be poor and the amount of air inclusions will increase. Further, it is desirable that the content of the low-polymerized molecule of a tetramer or less in the polystyrene sulfonate is 30% by weight or less. If it exceeds 30% by weight, the fluidity is lowered and the properties of the hydraulic body are impaired, which is not preferable.

The ratio of the aqueous emulsion (a) and the polystyrene sulfonate (b) is (a) / (b) in terms of solids weight ratio.
The ratio is 99.99 / 0.01 to 90/10, preferably 99.9 / 0.1 to 97/3, and more preferably 99.7 / 0.3 to 95/5.

When (a) / (b) is greater than 99.99 / 0.01, a large amount of lumps are generated when the hydraulic inorganic material, aqueous emulsion, water, fine aggregate and coarse aggregate are kneaded, and the strength of the cured product is It is not preferable because it is deteriorated, lacks fluidity, and has poor durability. Further, when (a) / (b) is smaller than 90/10, there are problems such that the original appearance of the cured body is impaired and the (warm) Mercury resistance of the cured body is reduced.

The compounding agent for hydraulic inorganic material of the present invention may be compounded at the time of compounding and kneading each of the above components with the hydraulic inorganic material,
Before and after the preparation of the aqueous emulsion (a) which is the first component of the essential components of the present invention, the mixture of the polystyrene sulfonate (b) which is the second component may be blended and kneaded into the hydraulic inorganic material.

Further, for the purpose of preventing the generation and promotion of rust of metals typified by iron and the like in the hydraulic inorganic material, and further enhancing penetration resistance, 1-hydroxy- represented by the following general formula:
Alkane-1,1-diphosphonic acid or a salt thereof may be mixed and kneaded.

[R; C _1-17 alkyl or alkenyl group, particularly preferably C _1-5 alkyl group].

Examples of the salt in this case include alkali metals, alkaline earth metals, amines, and alkanolamines. The amount of the 1-hydroxy-alkane-1,1-diphosphonic acid or a salt thereof is 0.01 to 10 with respect to the hydraulic inorganic material.
wt%, preferably 0.1-2 wt%.

The hydraulic inorganic material compounding agent of the present invention is added to the hydraulic inorganic material so as to be 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of cement. It is suitable to use.

If the blending amount is less than 1 part by weight, the wear resistance, strength, and durability of the hydraulic body cannot be improved. On the other hand, if the blending amount is too large, a large amount of lumps are generated, or the hydraulic inorganic compound (cement paste, (A mortar, concrete, etc.) is not preferable because it lacks abrasion resistance or becomes sticky.

In addition, the compounding agent for hydraulic inorganic material of the present invention, as required, nonionic, anionic or cationic polymer substance, coloring pigment, chelating agent, preservative, pH adjusting agent,
A plasticizer, an early strengthening agent, a slow hardening agent, a conductive (antistatic) agent and a reinforcing agent may be used as auxiliary additives.

Examples of the nonionic polymer include polyvinyl alcohol, dextrin, starch derivatives such as hydroxyethyl starch, and cellulose derivatives such as hydroxyethyl cellulose and hydroxypropyl cellulose.

Examples of the anionic polymer substance include anionized hydroxyethyl cellulose, anionized starch, anionized guar gum, anionized chitosan, carboxymethyl cellulose, anionized polyvinyl alcohol, polycarboxylic acid salts, and oxycarboxylic acid salts.

In addition, as the cationic polymer substance used in combination as needed, cationized hydroxyethyl cellulose, cationized starch, cationized guar gum, cationized chitosan, and cationic (meth) acrylamide,
Polymers such as dimethyldiallylammonium chloride are exemplified.

These nonionic polymer substances, anionic polymer substances and cationic polymer substances which are optionally used in combination may be appropriately used alone or in combination of two or more. It is suitable to use 0.05 to 5% by weight, preferably 0.1 to 3% by weight.

Examples of the color pigment include titanium white, titanium yellow, red iron oxide, iron book, ultramarine blue, chrome green, purple red iron oxide, and the like. As a chelating agent, ethylenediamine salt, 1-hydroxyethane diphosphate, as a plasticizer, phthalic acid ester, phosphoric acid ester, as an early strengthening agent, calcium chloride, as a slow hardening agent, gluconate, and as a strengthening agent. , Carbon fiber, polystyrene fiber, etc. can be used.

〔effect〕

Since the compounding agent for hydraulic inorganic material of the present invention comprises (a) an aqueous emulsion having an average particle diameter of 300 nm or less and having a crosslinked structure and (b) polystyrene sulfonate as essential components, a hydraulic inorganic material mixture is prepared. The fluidity at the time of kneading can be enhanced to prevent the occurrence of lumps, and further, the aesthetic appearance of the cured body (layer) of the hydraulic inorganic material can be enhanced. Further, various properties such as mechanical strength such as water resistance, agent resistance, and abrasion resistance can be further improved, and further, durability is remarkably excellent, so that the practical value thereof is extremely high.

Therefore, the compounding agent for hydraulic inorganic material of the present invention, a base material for the inner and outer walls of a building structure, an adhesive for tile application, a joint material for tile application, a flooring material, an anticorrosion lining material such as ALC rebar anticorrosion, water storage Waterproofing materials for tanks, pools, silos, bases for tennis courts, ship decks, pedestrian bridge decks, deck covering materials for bridge dyeing decks, acid-resistant fume pipes, special concrete molded products for GRC products, bus terminals, in tunnels, Semi-rigid roads in factories, spray protection coating materials for concrete skeletons that use carbon fiber, polyvinyl alcohol fiber, conductive coating materials that use carbon fiber, metal powder, electromagnetic wave shielding materials, ultra-high strength molded products, ship baust tanks, etc. Heavy duty anticorrosion coating materials, mortar floating repair materials, cable stayed bridge wire materials, decorative bottles, tiles, chemical molding of interlocking, etc. When used in preparing the exhibit very efficient performance.

〔Example〕

Next, in order to explain the present invention in more detail, examples are shown below.

Example 1 [Preparation of aqueous emulsion] An emulsifier shown in Table 1 was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction pipe, and a dropping funnel.
8.0 parts by weight and 150 parts by weight of water were charged and dissolved, and the system was replaced with nitrogen gas. Separately, 156 parts by weight of an unsaturated monomer mixture consisting of 90 parts by weight of ethyl acrylate, 60 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methyl roll acrylic acid amide and 1.5 parts by weight of water was prepared. Was added to the reaction vessel and emulsified at 40 ° C. for 30 minutes. Then 60 ° C
After the temperature was raised to 3.0, the polymerization initiator shown in Table 1 was potassium persulfate 3.0 × 10 ⁻³ mole / water phase, sodium thiosulfate 3.0 × 1.
KPS-redox type initiator (KPS type) or 2,2'-azobis (N, N'-dimethyllene) adjusted to be 0 ^-3 mole / water phase and copper sulfate 5.0 × 10 ^-5 mole / water phase Isobutylamidine hydrochloride (VA-044) was dissolved in 48.5 parts by weight of water so as to become 9.0 × 10 ^-3 mole / water phase, added to the above reaction vessel, and the remaining unsaturated monomer was immediately added. The solution was continuously added dropwise to the reaction vessel over 30 minutes, and polymerization was carried out at 60 ° C. After the addition of the unsaturated monomer was completed, polymerization was carried out at 60 ° C.
After completion of the dropwise addition of the unsaturated monomer, the mixture was aged at 60 ° C. for 90 minutes, cooled to room temperature, and adjusted to pH = 9 with triethanolamine to prepare an aqueous emulsion.

[Adjustment of polystyrene sulfonate]

Dichloroethane 58 was added to a reaction vessel equipped with a device similar to the glass reaction vessel used for preparing the aqueous emulsion.
5 parts by weight and 45 parts by weight of polystyrene (weight average molecular weight: 5,50
0) was added and dissolved by stirring at room temperature. Next, while maintaining the reaction temperature at 30 ° C., 35 parts by weight of anhydrous sulfuric acid was added dropwise, and after completion of the addition, aging was carried out at the same temperature for 30 minutes. After aging, the resulting polystyrene sulfonic acid was filtered, and the product was sufficiently dried under reduced pressure to distill off dichloroethane. First, the pH was adjusted to 3 with a 20% by weight aqueous calcium hydroxide solution. Then, the mixture was adjusted to pH 8 with 20 parts by weight of an aqueous sodium hydroxide solution, and adjusted to an aqueous solution having a solid concentration of 30% by weight, which was a polystyrene sulfonate calcium salt.

The active ingredient of the calcium salt of polystyrenesulfonic acid in the solid content thus obtained was 94.5%.

(Evaluation of aqueous emulsion)

The average particle size and crosslinkability of the aqueous emulsion obtained by the above method were measured by the following methods.

Average particle size: Coulter submicron particle analyzer (Coulter Electronics, USA, Coulter
(Model N4 type).

Bridgeability: 30 g of an aqueous emulsion adjusted to have a solid content of 40% by weight was cast uniformly on a 12 cm × 14 cm glass plate and air-dried at 25 ° C. The film thus obtained was cut into 2 cm × 4 cm pieces, dipped in a petri dish filled with benzene at 20 ° C. for 48 hours, and evaluated as follows based on the swelling degree and solubility of the film.

；: Equal to or slightly swelling with the film area (2 cm × 4 cm) before immersion in benzene.

Δ: The degree of swelling is large and the film shape is impaired.

X: The film was dissolved in benzene and turned into a uniform liquid.

(Preparation and performance evaluation of hydraulic inorganic material)

Silica sand, cement, water and the above-mentioned aqueous emulsion and polystyrene sulfonate were prepared at the following ratios to prepare a polymer cement mortar, and the fluidity, the amount of lumps, the thick coatability, the bleeding of the polymer, and the hardness of the polymer cement mortar were The appearance (aesthetic appearance), seawater resistance, solvent resistance, acid resistance and abrasion resistance were evaluated according to the following criteria.

No. 7 silica sand ^{* 1} 50 parts by weight No. 8 silica sand ^{* 1} 25 parts by weight Cement ^{* 2} 75 parts by weight Aqueous emulsion 11.25 parts by weight Polystyrene sulfonate 0.105 parts by weight Water 42.85 parts by weight Antifoaming agent 0.006 parts by weight ^{* 1} Waste water section Mining Machinery Co., Ltd. Diamond Sisand ^{* 2} Asano Cement (Portland Cement) made by Nihon Cent Co., Ltd. Fluidity: 56mm, 61mm, 66mm, 71mm, 76mm, ... on a glass plate with concentric circles with a radius of 5mm. Place a Viton hollow cone with a diameter of 30 mm and 50 mm, a height of 35 mm and a wall thickness of 3 mm, sufficiently break the polymer cement mortar so that there is no air entrainment in it, and immediately pull up this hollow cone, the polymer cement mortar Measures the casting length on the glass plate and the height of the polymer cement mortar.

Next, for the polymer cement mortar that has been sufficiently retained in the shape of a truncated cone, a mayonnaise bottle filled with silica sand to 1 kg is gently placed on the top surface of the polymer cement, a load is applied, and the polymer cement mortar is then added to the glass plate. The length cast on top and the height of the polymer cement mortar were measured.

Dama quantity: Thick coating: When the polymer cement mortar was sprayed or left pipe finishing was performed on the outer wall of the reinforced concrete building structure, the thickness of the polymer cement mortar when sagging did not occur was measured.

Polymer bleed-out: 500 g of polymer cement mortar immediately after preparation was placed in a beaker 1 and allowed to stand for 10 minutes, and then the presence or absence of polymer bleed in the upper layer of the polymer cement mortar was visually determined.

Aesthetic appearance: The exterior wall sprayed or plastered with polymer cement mortar was visually judged 28 days after the material age.

Water-resistant, sea-water-resistant, solvent-resistant: Polymer cement mortar 250 immediately after preparation is evenly filled into a 150 ml desposal cup (PP) manufactured by Inouchi Seieido Co., Ltd. so that air is not mixed.

Then, after leaving still for 2 days, the mold was cut out, left still at room temperature for 26 days (material age), and the cured product was placed in a 500 ml beaker filled with 25 ° C tap water, seawater and benzene for one year. After immersion, the state of the surface of the cured product was observed and evaluated according to the following criteria.

；: The mortar surface is as glossy as the specimen before immersion.

Δ: The mortar surface has no gloss.

X: The mortar surface is whitened.

Acid resistance: A specimen equivalent to that used for the measurement of water resistance and seawater resistance after 28 days of aging was immersed in a 1% by weight aqueous sulfuric acid solution for 28 days, and evaluated according to the following criteria.

；: The surface of the specimen was slightly whitened as compared to the specimen before immersion, but there was no change in shape.

Δ: The specimen surface was whitened, and the surface of the shape was slightly eroded.

×: The surface of the specimen was significantly whitened, the erosion was remarkable, and the shape was damaged.

Abrasion resistance: Using the above mortar composition, a cured product was prepared into a 50 mmφ × 50 mm cylindrical shape, and after 28 days of material age, the cured product was placed on a 10-mesh screen and subjected to a low tap shaking method. Shaking was carried out for 2 minutes (manufactured by Heiko Seisakusho Co., Ltd.), and the wear resistance was evaluated by the following formula.

A: Weight before shaking (g) B: Weight after shaking (g) Durability: A core equivalent to that used for the evaluation of abrasion resistance was put in an autoclave of 10 and the pressure was reduced to 10 mmHg or less. After confirming that there was no leak, carbon dioxide gas was introduced into the autoclave to a concentration of 5%, and then the pressure was adjusted to normal pressure with air.
The temperature and humidity were adjusted so as to be% RH, and the mixture was allowed to stand for 1 month.
After standing, the core was cut into a semi-cylindrical shape, a 1% phenolphthalein-alcohol solution was sprayed on the cut surface, the depth at which the cut surface turned red was measured, and evaluated according to the following criteria. .

○: The cut surface of the cured product is entirely red, or 0.
It is reddish from 2 to 0.5 cm divided into deep parts.

Δ: Reddish from 0.6 to 1.0 cm or more of the surface of the cured body to a deep portion.

×: Red or red in the cut surface from 2.0 cm to the deep part of the surface of the cured product.

The properties of the aqueous emulsion thus obtained and the performance of the polymer cement mortar are shown in Table 1.

Documents Nos. 1 to 4 are examples of the present invention, and are found to be good as compounding agents for hydraulic inorganic materials.

 Sample Nos. 5 to 7 and 7'are comparative examples.

Example 2 Stearyl 2-hydroxy-3-allyloxy-1-
4 parts by weight of propylsulfosuccinate triethanolamine salt, 1.96 parts by weight of branched chain alkylbenzenesulfonic acid triethanolamine having 10 to 14 carbon atoms, 0.04 parts by weight of xylenesulfonic acid triethanolamine salt, polyoxypropylene poly 2.0 parts by weight of oxyethylene PP'-isopropylidene diphenyl ether dimethacrylate (PO = 2, EO = 18) as an emulsifier, 135 parts by weight of ethyl acrylate, 15 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methylolacrylamide Department and water
An aqueous emulsion was prepared by subjecting 1.5 parts by weight of the unsaturated monomer to emulsion polymerization in the same manner as in Example-1.

On the other hand, partially hexylated polystyrene obtained by alkylating polystyrene having a weight average molecular weight of 7,000 by 20% was sulfonated in the same manner as in Example 1, and neutralized with triethanolamine to obtain a partially hexylated polystyrene sulfonic acid triethanolamine salt. Got (Sulfonation rate 86
%) Next, these (a) aqueous emulsions were blended with (b) partially hexylated polystyrene sulfonate in a solid content weight ratio as shown in Table 2, and this was added to a polymer cement mortar having the same ratio as in Example 1. Prepared. Then, the performance as a polymer cement mortar was evaluated in the same manner as in Example 1. Table 2 shows the results. Materials Nos. 9 to 11 are examples of the present invention, and it is found that the mixing ratio of the aqueous emulsion and polystyrene sulfonate is preferably 99.99 / 0.01 to 90/10.

 Sample Nos. 8 and 12 are comparative examples.

Example 3 The following emulsifiers E-1 and E-2 shown in Table-3, and By adjusting the unsaturated monomer mixture M-1 and M-2 shown below, Emulsion polymerization was carried out under the conditions shown in Table 3 according to Example 1,
An aqueous emulsion was obtained, the pH of which was adjusted to 9 with triethanolamine.

On the other hand, a copolymer having a weight average molecular weight of 20,000 and a molar ratio of styrene and maleic anhydride of 2.0 was subjected to sulfonation in the same manner as in Example 1 to obtain polystyrenesulfonic acid-maleic anhydride triethanolamine salt. The sulfonation rate of this styrene was 92.5%.

Example 1 was then carried out using a formulation for hydraulic inorganic material which was formulated so that the weight ratio of solid content to aqueous emulsion / polystyrene sulfonic acid-maleic anhydride = 99.5 / 0.5.
Polymer cement mortar was prepared in the same manner as above, and its performance was evaluated. The results are shown in Table-3. Sample Nos. 13 to 16 are examples of the present invention, and it is understood that the polymer cement mortar to which the compounding agent for hydraulic inorganic material of the present invention is added has excellent thixotropic properties. Sample Nos. 17 to 18 are comparative examples.

Example 4 The flow of concrete was carried out in accordance with the Architectural Institute of Japan JASS5T-402 using a compounding agent for a hydraulic inorganic material having a solid content weight ratio of the aqueous emulsion of Example 2 and polystyrene sulfonate of 97.72 / 2.28. The concrete was evaluated for its properties, and the concrete was molded according to JIS A 1108.
After 28 days, the durability (neutralization test) was evaluated according to Example 1.

The above concrete had excellent mechanical strength such as fluidity, compressive strength, bending strength, etc. and reddishness in the neutralization test on the entire cut surface of the hardened concrete, and was excellent in durability, as compared with the base concrete containing no additive. .

Example 5 A polymer cement mortar was prepared in exactly the same manner as in Example 1 except that 0.3 part by weight of 1-hydroxyethane-1,1-diphosphonic acid was further added in the preparation of the hydraulic inorganic material of Example 1.

Example 6 In the preparation of the hydraulic inorganic material of Example 1, 0.15 weight of polystyrenesulfonic acid triethanolamine salt (however, the amount of triethanolamine is 1.2 times equivalent of sulfonic acid group) was used in place of the polystyrenesulfonic acid Ca salt. Parts and 1-hydroxyalkane-1-diphosphonic acid or 1-hydroxyalkane-1-diphosphonic acid triethanolamine salt shown in Table 4 (however, the amount of triethanolamine is 4.2 times that of the phosphonic acid group). Polymer cement mortar was prepared in exactly the same manner as in Example 1 except that 0.3 part by weight of (equivalent weight) was added.

For the polymer cement mortars obtained in Examples 5 and 6 above, rust prevention was measured according to Annex 2 of JIS A6205 [Test method for accelerated corrosion of reinforcing steel in concrete]. Table 4 shows these results. In addition, in the preparation of the hydraulic inorganic material of Example 1, a sample prepared by preparing polymer cement mortar in exactly the same manner as in Example 1 except that polystyrene sulfonate was not added was used as a comparative example (Sample No.
26), ⊚ when rust was significantly less than this, ∘ when less, and × when the same.

Claims (1)

(57) [Claims] 1. A compounding agent for a hydraulic inorganic material, comprising an aqueous emulsion having an average particle diameter of 300 nm or less and having a crosslinked structure and polystyrene sulfonate as essential components.