JPH01164747A - Compounding ingredient for hydraulic inorganic material - Google Patents

Abstract

PURPOSE:To obtain the title compounding ingredient giving hydraulic inorg. material hardened body having excellent beauty, water resistance, solvent resistance and mechanical property, and exhibiting stable dispersibility for a long period, by emulsion polymerizing unsatd. monomer in the presence of emulsifier consisting of specified three components as essential component. CONSTITUTION:The emulsifier is prepd. by using at least three components, one or more kinds of reactive emulsifier (A) of formula I-III [where, R10 is C2-4 alkylene group, R11 is R13, phenyl group, NH2 or COOH, R12 is H or CH3, R13 is (substd.)hydrocarbon residue, a1 and a3 are 0-50, M is mono- or di-valent cation and m is ion valence of M], sulfonate type emulsifier (B) of formula IV (where, R14-15 are H or C1-20 alkyl group) and poly(metha)acryloyl type emulsifier (C) of formula V (where, R16 is R12 and a4 is 1-50) as essential component, and by mixing these components in the proportion of A/C=(9/1)-(1/9) and B/A+C=(7/3)-(1/9). Then, the unsatd. monomer is emulsion polymerized in the presence of 0.1-15wt.% the emulsifier above-mentioned to obtain the compounding ingredient having <=100nm mean particle size, crosslinked structure, glass transition temp. higher than one calculated by weight fraction method and <=-30mV zeta-potential.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a formulation for hydraulic inorganic materials containing an aqueous emulsion as a main component.

[Prior art]

Conventionally, for hydraulic inorganic compositions such as cement paste, mortar, plaster, concrete, and grout,
The intention is to improve its adhesive strength, waterproofness, chemical resistance, mechanical strength such as bending strength and tensile strength, or abrasion resistance.
Furthermore, many proposals have been made to add various compounding agents to improve the appearance of these molded products and increase their added value.

For example, JP-A-60-103061, JP-A-60-2
No. 51160, JP-A-60-173054, JP-A-5
7-67061, JP-A No. 57-77059, JP-A-59-102480, JP-A-58-49653, etc., disclose the use of styrene and vinyl chloride for hydraulic inorganic compositions such as mortar and cement. - Various polymers such as combinations of polymer emulsions such as ethylene binary copolymer emulsions, ethylene-hinyl acetate copolymer emulsions, synthetic rubber latexes such as styrene-butadiene and styrene-butadiene-methyl methacrylate, and composite polymer emulsions. The addition of compound formulations is disclosed.

Although these conventional methods can improve the physical properties and appearance of the hydraulic inorganic composition described above, these properties have not yet been fully satisfied.

〔the purpose〕

The purpose of the present invention is to provide excellent dispersion stability over a long period of time, and unlike the conventional compounding agents described above, to have excellent miscibility (impregnability) with hydraulic inorganic materials, and to improve the aesthetic appearance of the cured product of hydraulic inorganic materials. The object of the present invention is to provide a compounding agent for hydraulic inorganic materials that can further improve various performances such as water resistance, solvent resistance, and mechanical properties.

〔composition〕

According to the present invention, the average particle size is 1100 nm or less, has a crosslinked structure, has a glass transition temperature higher than the value calculated by the weight fraction method, has a zeta potential of 130 mV or less, and has dispersion stability. Provided is a compounding agent for hydraulic inorganic materials which is characterized in that it contains as an essential component an aqueous emulsion that exhibits excellent properties over a long period of time.

First, the aqueous emuldigon, which is the island edge component of the formulation for hydraulic inorganic materials of the present invention, has an average particle diameter of 1100.
It is characterized in that it is less than n, preferably less than 80 nm.

In an aqueous emulsion, a film is essentially formed by filling and fusing particles, so the average particle size is required to be small, but in the present invention, as described above, the average particle size is 1100 nm or less. , is preferably limited to 80 nm or less, so it has good immersion properties in hydraulic inorganic materials, good heat fusion, transparency of the film and inorganic cured product,
It is possible to improve various properties such as smoothness and gloss to a large extent.Also, since it has a lobby property, it is possible to improve the adhesion between the hydraulic inorganic material and the aqueous emulsion composition of the present invention. becomes good.

If the average particle size exceeds 1100 nm, the fusion properties (denseness) when forming a film will be poor, and the film and mineralized product may lack gloss, transparency, and smoothness, or the aqueous The permeability of the emulsion to the hydraulic inorganic material is also poor, and furthermore, the aqueous emulsion bleeds out, making it impossible to achieve the intended purpose of the present invention.

A second feature of the aqueous emulsion, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, is that it has a crosslinked structure within and/or between its particles.

That is, the aqueous emulsion, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, has internal and/or interparticle relationships between the functional groups of the raw unsaturated monomers, or between these and the functional groups of the emulsifier. Groups have ionic bonds, hydrogen bonds,
Since it is crosslinked by a condensation reaction or polymerization reaction, it is possible to form a film with excellent transparency, adhesiveness, water resistance, solvent resistance, and mechanical strength.

Furthermore, the third characteristic of the aqueous emulsion, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, is that it has a glass transition temperature higher than the value calculated by the weight fraction method.

Glass transition temperature (Tg) is the temperature at which a polymer changes from a glassy, hard state to a rubbery state when heated.If the glass transition temperature of a component, which is a structural factor of a polymer, is known, The glass transition temperature can be determined from the following equation using the weight fraction method.

Tg TgA TgB WA; Weight fraction of component A WB; Weight fraction of component B TgA; Glass transition temperature of component A TgB; Glass transition temperature of component B This glass transition temperature is influenced by various structural factors and is generally It is known that the glass transition temperature of a polymer having a crosslinked structure increases, and that adding a plasticizer to the polymer lowers the glass transition temperature.

On the other hand, for aqueous emulsions, the minimum film-forming temperature is known as the lowest temperature at which a film is formed by filling and fusing particles, and there is a proportional relationship between this minimum film-forming temperature and the glass transition temperature. It has been known.

As mentioned above, the aqueous emulsion of the present invention has a film-forming ability that shows a glass transition temperature higher than the value calculated by the weight fraction method, and has a dense crosslinked structure, so it has transparency, adhesiveness, and smoothness. The transparency of the cured product of the hydraulic inorganic material is excellent because it can form a film that is hard, has excellent mechanical strength such as tensile strength, and modulus strength, and has excellent water resistance and solvent resistance. Mechanical strength such as smoothness, water resistance, chemical resistance, and abrasion resistance can be improved.

The fourth characteristic of the aqueous emulsion, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, is that the zeta potential is -
It has a value of 30 mV or less, preferably -50 mV or less.

In general, dispersed colloidal particles such as aqueous emulsions have a system that surrounds the particles at the interface between the particles and the solution, and the interfacial potential (
This charge repels colloidal particles and maintains a stable system.If this zeta potential is negatively charged, it is required to be lower. As mentioned above, the polymer latex of the present invention has a zeta potential of 130 mV or less, preferably 150 mV or less.
The colloidal particles in the dispersion exhibit extremely high stability since they have the following values:

The fifth feature of the aqueous emuldimine, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, is that it has excellent dispersion stability over a long period of time.

That is, the aqueous emulsion according to the present invention has an average particle size of 1
100n or less, but this one is heated at 45°C1
Even when subjected to a forced heating dispersion stability test for one week, there was virtually no change in the average particle size, and even if there was a change, it was usually a single peak distribution of particles with an average particle size of 150 nm or less. Even when the particle size distribution is large and the rate of change is large, the particle size distribution of the first peak with an average particle diameter of less than 150 nm is 97% or more, and 2.
The grain shows a bimodal distribution in which less than 3% of particles have a particle size distribution of 300 nm or more, and the particle size fraction of the average particle diameter is extremely small.

Furthermore, the aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic materials of the present invention, shows no signs of failure even when subjected to a long-term dispersion stability test at 25°C for 6 months. Moreover, the rate of change in the average particle diameter is extremely small.

Therefore, the aqueous emulsion according to the present invention substantially does not coalesce or agglomerate particles with each other over time, and does not generate coarse particles. Since there is no change in viscosity or change in appearance, it shows excellent dispersion stability over a long period of time, and when a film is formed, there is no decrease in mechanical strength due to the formation of coarse particles. .

The reason why the aqueous emulsion, which is an essential component of the formulation for hydraulic inorganic materials of the present invention, exhibits excellent dispersion stability as described above is not necessarily clear, but since its average particle size is 1100 nm or less, the particles In the present invention, Brownian motion between sulfonate emulsifiers is relatively active, and undesirable side reactions such as polymerization reactions and crosslinking reactions that are caused by polymerizable or reactive emulsifiers remaining in the system are avoided. It is clear from the drawings that the reactive emulsifiers are regularly arranged and furthermore,
In the process of emulsion polymerization, there is little by-product of low-molecular (low-boiling point) compounds other than unsaturated monomers used as raw materials and/or low-boiling point compounds that are thought to promote coalescence and aggregation between particles. Because of this, side reactions such as polymerization reactions and crosslinking reactions are suppressed, and each particle is sufficiently protected, so coalescence and aggregation of particles are prevented and the formation of coarse particles is not promoted. point is presumed to be the fundamental factor.

In the present invention, in order to improve the dispersion stability of the aqueous emulsion, for example, P-hydroxydiphenylamine, N,N'-diphenyldiamine, 2,
Conventionally known polymerization inhibitors and polymerization terminators such as 5-di-tert-butylhydroquinone can also be added.

In addition, the average molecular weight of the aqueous emuldigone, which is an essential component of the compounding agent for hydraulic inorganic materials of the present invention, is generally several hundred thousand or more, often from several thousand blades to several hundred million, and has a high degree of crosslinking. In some cases, the molecular weight is even higher than this, on the order of tens of millions to 1 billion.

The present invention will be explained in more detail below.

The water-free emulsion used as a compounding agent for hydraulic inorganic materials in the present invention can be obtained by emulsion polymerization of unsaturated monomers in the presence of a specific emulsifier described below.

Examples of the unsaturated monomer include nine (meth)acrylic esters represented by the following general formula (I) (where R1 and R
2 is hydrogen or a methyl group, R3 is an alkyl group having 1 to 18 carbon atoms), lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylonitrile,
Nitriles such as methacrylonitrile, styrene, α-
Styrenes such as methylstyrene and chlorostyrene, vinyls such as vinyl chloride and vinyl bromide, alkyl vinyl ethers such as vinylidene chloride, methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, vinylidenes such as vinylidene bromide, butadiene, chloroprene, Examples include dienes such as isoprene and vinylpyridine, but it is preferable to use (meth)acrylic acid esters, lower fatty acid vinyl esters, nitriles, and styrenes.

In addition, in the present invention, the unsaturated monomer to be copolymerized with the above unsaturated monomer is used to further strengthen the crosslinking structure within and/or between particles of the aqueous emulsion to be produced, and to form a film. Sometimes unsaturated monomers with reactive functional groups are preferably used to promote crosslinking, but even unsaturated monomers without reactive functional groups have active hydrogen in emulsion polymerization systems. It is also possible to use unsaturated monomers which can be converted into compounds.

Examples of unsaturated monomers having such reactive functional groups include compounds represented by the following general formulas (n) to (■). These monomers can be used alone or in combination of two or more, and if necessary, other copolymerizable unsaturated monomers can also be used in combination.

90H (wherein, R, TR21R41Rs IRRIR'l T
Rl1. R91BIDIEltl lR2 and tl are as follows.

RllR21; hydrogen atom or methyl group R4; carbon number 2
-4 alkylene group R5; direct bond, alkylene group having 1 to 3 carbon atoms, phenylene group or substituted phenylene group RGi oxygen atom or -NH- R7; hydrogen, alkylol group having 1 to 5 carbon atoms RIl; hydrogen, carbon Alkylol group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
Alkyl group R9; Alkylene group A having 1 to 4 carbon atoms; Methylene group or carbonyl group B; -CH,0- or carboxyl group; hydrogen atom, alkyl group having 1 to 3 carbon atoms, C0NHC0NH2 E; hydrogen atom , an alkyl group having 1 to 3 carbon atoms or -CH
, C00H tl; real number R2 of 1 to 20; integer t of 0 or 1; integer of 0 to 10) General formula (II), (III), (rV). (V), (V
Specific examples of compounds I), (■) and (■) include those shown below.

Examples of general formula (It) Glycidyl acrylate Glycidyl methacrylate Glycidyl clo 1-nate Glycidyl allyl ether Examples of general formula (m) Hydroxyethyl acrylate Hydroxyethyl methacrylate Hydroxyethyl crotonate Hydroxypipyl acrylate Hydroxypipyl methacrylate Hydroxypipill Crotonate Hydroxybutyl acrylate Hydroxybutyl methacrylate Polyoxyethylene monoacrylate Polyoxyethylene monomethacrylate Polyoxyethylene monocrotonate Polyoxypropylene monoacrylate Polyoxypropylene monomethacrylate Polyoxypropylene monocrotonate Polyoxybutylene monoacrylate Polyoxybutylene monocroto nate hydroxyethyl allyl ether hydoxybutyl allyl ether hydroxybutyl allyl ether polyoxyethylene allyl ether polyoxypropylene allyl ether polyoxybunalene allyl ether Example of general formula (IV) allylamine acrylamine methacrylamine aminostyrene α -Methylaminostyrene Example of general formula (V) AcrylamideMethacrylamide-15-aminopyrmethacrylamideMonomethylacrylamideMonoethylacrylamideDiethylolaminoprobyl acrylamideGeneral formula (V
Examples of l) Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, fumaric acid and its monoester or anhydride of an alkyl group having 1 to 5 carbon atoms, maleic acid Alanidofumaric acidAlanidN-Canolebamoylmaleic acidamideN-Carbamoylfumaric acidamideExample of general formula (■)MethylallylthiolMethylmercaptostyrene-16-1Example of general formula (■)N-Methylolacrylic acidamideN-Methylolmethacrylic Acid amide N-methylol crotonic acid amide N-(2-hydroxyethyl)acrylic acid amide N-(
2-hydroxyethyl) methacrylic acid amide N-(2-
Hydroxybutyr) Acrylic Acid Amide N-(2-Hydroxybutyr) Methacrylic Acid The ratio of the above unsaturated monomer and the unsaturated monomer having a reactive functional group is 9
9/1 to 60/40 (weight), preferably 99/
1 to 90/10 (weight). This usage rate is 997
If it is thicker than 1, the degree of crosslinking within and between particles of the aqueous emuldigone produced will be small, and if it is smaller than 60/40, emulsion copolymerizability will be poor, and a large amount of aggregates will be produced, or film-forming properties will be poor. Cracks and streaks may occur in the formed film.

In the present invention, the following general formulas (IK), (X), (X[
), (Xll), (xm) and (XIV); a sulfonate emulsifier represented by general formula (XV); and a polyoxyalkylene represented by general formula (XVI). It is necessary to use an anionic emulsifier consisting of at least three components of ethylenically unsaturated carboxylic acid polyesters (hereinafter abbreviated as poly(meth)acroyl type emulsifier).

803M1/m (wherein, Lo-R1,1, R12, R13, R14, R
1,,, al, a2, a3, a4, a, m and G are as follows.

R,o; Alkylene group having 2 to 4 carbon atoms R1□; Hydrocarbon group, phenyl group, amino group or carboxylic acid group that may have a substituent R121RIG; Hydrogen or methyl group R,3; ffi
Hydrocarbon group Rt4+R1s which may have a substituent; hydrogen or an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably one of Rl4 or RlE is hydrogen and the other is Those with 6 to 18 carbon atoms a□1821831a4 ; Indicates the average number of moles added/added 8
1.8□la3; Real number from O to 5o a4; Real number from 1 to 50, preferably the number of moles of alkylene group oxide added in the molecule is 8 or more M; Monovalent or divalent cation m; Ionic valence of M ○ -o-p-〇- ■ ・OR1,l ll ○R180R11IOR1R OCnHzn-g+ (Rls) & O-R□GIR□
7; Hydrogen or alkyl group having 1 to 2 carbon atoms R, 8; Hydrogen or (Rto O←H or gl; Integer g2 of 0 to 5; Integer n of 0 to 10; Integer 8 of 1 to 10; 1 to 50 real numbers (CH,)2-CH@- or (CH3)2'-CH-
@-CH2- and y: real number Lq of 1 to 5 1R2 (1; hydrogen or alkyl group having 1 to 20 carbon atoms Y/, alkylene group having 3 to 8 carbon atoms, oxygen or carbonyl group) Also, these emulsifiers has an ultrafine average particle size and a dense crosslinked structure within and/or between particles,
It forms a film that exhibits a glass transition temperature higher than the value determined by the calculation formula, and also has excellent dispersion stability that suppresses coalescence and aggregation of particles over a long period of time when the zeta potential is 130 mV or less. In order to obtain an ultrafine particle pre-crosslinked aqueous emulsion, (a) the above general formulas (IX), (X), (XI),
At least one reactive emulsifier represented by (X[l), (xm) and (XIV); (b) a sulfonate emulsifier represented by general formula (XV); and (c) a sulfonate emulsifier represented by general formula (XV).
At least three components of the poly(meth)acroyl type emulsifier represented by I) are essential components, and (a)/(c)=971~
179 weight ratio, preferably 471 to 1/4 weight ratio, (b
)/(a)+(c) Used in a 7/3-1/9 weight ratio, preferably in a 372-1/4 weight ratio.

If the usage ratio of (a)/(c) is greater than 971,
The crosslinkability and (or stability of the dispersion cylinder) of the aqueous emulsion produced may deteriorate, and if it is smaller than 1/9, a large amount of aggregates may occur during emulsion polymerization, or the average particle size of the aqueous emulsion produced may become large. There is.

Also, the usage ratio of (b) / (a) + (c) is 773
If it is larger than 1/9, the degree of crosslinking within and/or between particles of the aqueous emulsion to be produced becomes small, resulting in poor transparency, water resistance and solvent resistance, and if it is smaller than 1/9, unsaturated monomer microemulsification or solubilization is lacking, the average particle size of the resulting aqueous emulsion becomes large, and as the emulsion polymerization progresses, particles coalesce and aggregate to become cloudy, and even transparent or translucent ultrafine particles Even if an aqueous emulsion is formed, the zeta potential is negative and small, and if stored for a long period of time, the particles will easily coalesce and aggregate, producing coarse particles and becoming extremely cloudy.
Furthermore, the aqueous emuldigone may undergo phase separation or its viscosity may increase significantly.

When these emulsifiers are used in the above proportions, they become ultrafine particles, have a crosslinked structure, exhibit a glass transition temperature higher than the value calculated by the weight fraction method, have a highly negative zeta potential, and It is possible to produce an aqueous emulsion with excellent dispersion stability in which coalescence and aggregation of particles are suppressed over a long period of time.

The appropriate amount of these emulsifiers to be used is about 0.1 to 15% by weight based on the unsaturated monomer to be emulsion polymerized, preferably 0.5 to 10% by weight.

Additionally, known anionic, nonionic and cationic surfactants may be added as necessary, specific examples of which include higher alcohols, higher alcohol oxidized alkylene adducts, alkylphenol oxidized alkylene adducts, and styrenated surfactants. Sulfate type of phenol alkylene oxide adduct, olefin sulfonate type such as α-olefin, long chain alkyl amine alkylene oxide adduct and di-long chain alkyl amine alkylene oxide adduct
Ammonium salt form, sodium salt of N-(1,2-dicarboxyethyl)-N-octadecylsulfonic acid monoamide, dialkyl sulfosuccinate, bleached ceramic resin, 4-hydroxy-4,5-dicarbonepentadecanoic acid or 4,5 Examples include organic and inorganic salts of -dicarboxy-pentadecanoloid.

In particular, when aggregates (clumps) are formed in a mixture of a hydraulic inorganic material (cement, gypsum, etc.) and the aqueous emulsion of the present invention, the polyoxyethylene (polyoxypropylene) alkyl phenyl ether, Adding a nonionic surfactant such as oxyethylene (polyoxypropylene) alkyl ether or polyoxypropylene ethylene glycol to the emulsifier compositions (a), (b) and (c) above is effective in suppressing lumps.

In order to obtain the aqueous emulsion which is the compounding agent for hydraulic inorganic materials of the present invention, a conventionally known emulsion polymerization method can be used as is in the presence of the unsaturated monomer and the emulsifier.

For example, in the presence of a polymerization initiator corresponding to 0.1 to 5% by weight of the unsaturated monomer, a polymer of 10 to 6
It may be emulsified and dispersed in water at a concentration of 0% to carry out emulsion polymerization.

As the polymerization initiator, water-soluble independent initiators and water-soluble redox initiators used in ordinary emulsion polymerization are used, such as hydrogen peroxide alone or hydrogen peroxide and tartaric acid, citric acid, Combinations with carboxylic acids such as ascorbic acid, hydrogen peroxide, oxalic acid, sulfinic acids and their salts or oxydialdehydes,
In addition to combinations with water-soluble iron salts, persulfates, percarbonates,
Peroxides such as perborates and 2,2'-azobis(2
-amidinopropane) and its salts, 2,2'-azobis(
Water-soluble azo initiators such as N,N'-dimethylene-imbutyramidine) and its salts, and 4,4'-azobis(4-cyanovaleric acid) and its salts can be used.

In particular, when the above-mentioned water-soluble azo initiator is used, it is easy to prepare an aqueous emulsion, which is a compounding agent for hydraulic inorganic materials of the present invention.

In addition, a water-soluble nonionic polymeric substance, an anionic polymeric substance, and further a cationic polymeric substance can be used in combination if necessary. Furthermore, plasticizers and pH adjusters commonly used in conventional methods can also be used in combination, if necessary.

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

Examples of anionic polymeric substances include polymers such as anionized hydroxyethyl cellulose, anionized starch, anionized guar gum, anionized chitosan, carboxymethyl cellulose, and anionized polyvinyl alcohol.

In addition, cationic polymer substances used in combination as necessary include cationized hydroxyethyl cellulose, cationized starch, cationized guar gum, cationized chitosan, and heavy polymers such as cationic (meth)acrylic acid amide and dimethyldiallylammonium chloride. One example is merging.

These nonionic polymeric substances, anionic polymeric substances, and cationic polymeric substances used in combination as necessary can be used alone or in combination of two or more, but the amount of addition is determined by It is appropriate to use 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on the weight of the polymer.

Further, as the plasticizer, phthalate ester, phosphate ester, etc. can be used. Furthermore, as a pH adjuster, salts such as sodium carbonate, sodium bicarbonate, and sodium acetate are used.
．． They can be used together in a range of 0.01 to 3% by weight.

In order to obtain a hydraulic inorganic material using the compounding agent according to the present invention, the specific aqueous emulsion is added to a hydraulic inorganic composition such as cement paste, mortar, plaster, concrete, grout, etc. The auxiliary additive components may be mixed and then cured by known means.

The auxiliary additive components used in the present invention include coloring pigments, early strength agents, dispersants, waterproofing agents, antifoaming agents, antifreeze agents, preservatives, conductive (antistatic) agents, reinforcing agents, and the like.

In this case, examples of the colored pigment include titanium white, oxide yellow, titanium yellow, red iron black, iron black, ultramarine blue, chrome green, and purple red iron black.

In addition, calcium chloride is used as an early strength agent, lignin sulfonate-based and oxycarboxylate-based dispersants are used, calcium stearate is used as a waterproofing agent, and tributyl phosphate and polyester are used as antifoaming agents. Oxyalkylene glyco=28=1, polyoxyalkylene alkyl ether, polyoxyalkylene (di)alkylphenyl ether, etc. are used as antifreeze agents, nitrogen-containing sulfur compounds are used as conductive (
As the antistatic agent, metal powder such as iron powder or copper powder or carbon black can be used, and as the reinforcing agent, carbon fiber,
Glass fiber, synthetic resin fiber, etc. can be used.

〔effect〕

The compounding agent for hydraulic inorganic materials of the present invention has an average particle size of 1
100N or less, has a crosslinked structure, has a glass transition temperature higher than the value calculated by the weight fraction method, and has excellent dispersion stability over a long period of time. Unlike compounding agents for hydraulic inorganic materials, it can improve the appearance of the cured product of hydraulic inorganic materials, and improve water resistance, solvent resistance, and mechanical strength such as bending strength, compressive strength, and abrasion resistance. It has extremely high practical value because it can further improve various performances.

Therefore, hydraulic inorganic material compositions such as polymer cement mortar (concrete) and plaster using the compounding agent for hydraulic inorganic materials of the present invention can be used as exterior (repair) materials for buildings, tiling adhesives, warehouses, passageways, etc. , flooring materials for livestock farms, gas stations, etc., anticorrosive linings for ALC reinforced factory floors, waterproofing agents for water storage tanks, pools, silos, tennis court bases, etc., deck covering materials for ship decks, bridge decks, etc., acid-resistant Huyum pipes, special concrete molded products such as GRC products, bus terminals, semi-rigid paths in tunnels, spraying of concrete structures require protective coatings, color conductive coating materials, electromagnetic shielding materials, ultra-strong molded products, heavy duty It is excellent as an anti-corrosion coating material, mortar floating repair, grouting material for cable-stayed bridge wire, etc., coating material for cosmetic molded products such as decorative skins, tiles, and interlocking.

〔Example〕

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

Example 1 Emulsifier 8 shown in Table 1 was placed in a glass reaction vessel equipped with a thermometer, stirrer, reflux condenser, nitrogen introduction tube and dropping funnel.
parts by weight and 150 parts by weight of water were charged and dissolved, and the inside of the system was purged 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-methylolacrylamide and 1.5 parts by weight of water was prepared. 15 parts by weight were added to the reaction vessel and emulsified at 40°C for 30 minutes. Then, after raising the temperature to 60°C, polymerization initiator 2,
9. 2'-azobis(N,N'-dimethyleneisobutyramidine) hydrochloride. OX 10-3mo Q,e/water was dissolved in 48.5 parts by weight of water as above the aqueous phase and added to the reaction vessel, and the remaining unsaturated monomer was immediately poured into the reaction vessel for 30 minutes. It was continuously added dropwise and polymerization was carried out at 60°C. After dropping the unsaturated monomer, the temperature was 60°C at 60°C.
Aged for minutes.

[Evaluation of water-based emulsion]

The average particle diameter, crosslinkability, zeta potential, film forming property, glass transition temperature, and film properties of the aqueous emulsion thus obtained were measured by the following methods.

Average particle size: Coulter Submicron Particle Analyzer (Coulter Electronics, Inc., USA)
The average particle diameter was measured using a ter Model N4 type.

Crosslinking property: 30 g of an aqueous emulsion adjusted to have a solid content of 40% by weight was uniformly cast on a 12 cm x 14 ann glass plate, and air-dried at 25°C. The film thus obtained was cut into 2 cm x 4 cm pieces and placed in a Petri dish filled with benzene at 20°C.
The film was immersed for a period of time and evaluated based on the degree of swelling and solubility of the film as shown below.

○; Film area before immersion in benzene (2cm x 4cm
It is the same as m) or slightly swollen.

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

×: The film was dissolved in benzene and became a uniform liquid.

Zeta potential: Laser rotating prism type colloidal particle zeta potential measuring instrument (LA manufactured by PENKEN INC, USA)
The zeta potential was measured using a SERZEETM Model 500).

Film forming property: A film was formed by air drying at 25°C, and the condition of the formed film was visually evaluated.

○: Forms a smooth and uniform film.

△: Forms a film with a reticulated surface.

X: No film is formed.

Glass transition temperature (Tg) Seiko Electronics Co., Ltd. thermal analysis measurement device (SSC5000)
Tg was measured using DSC200). The calculated value of Tg was calculated by the weight fraction method (described above).

[Evaluation of film characteristics]

The above aqueous emulsion 3 with solid content adjusted to 20% by weight
0 parts by weight was uniformly cast onto a 12 cm x 14 cm glass plate, air-dried at 25°C to form a film, and the film properties were evaluated. Film properties were evaluated based on the following criteria.

Transparency: According to JIS K 6714, the haze value of the film was measured using an integral light transmittance measuring device.

Water resistance: The film was cut into pieces of 2 cm x 4 cm, immersed in a Petri dish filled with water at 20°C, and the time until the film turned white was visually determined.

0: 10 days or more Δ: 2 days or more, less than 10 days ×: Less than 2 days Adhesion: The surface of the film was touched with a finger, and the sticky feeling was evaluated according to the following criteria.

○; No sticky feeling △; Slightly sticky ×; Sticky elongation and strength; The modulus strength was measured.

[Preparation and performance evaluation of hydraulic inorganic materials] JIS A62
According to 04 (1982), Nippon Cement ■ Asanocement 475Kg/rn', fine aggregate (specific gravity: 2.64
, coarse grinding rate: 2.42) 950Kg/rn', aqueous emulsion with an addition amount of 20wt and a flow value of 140±5
A mortar composition made by adding water so that
Appearance, bending strength, compressive strength, abrasion resistance, water resistance, seawater resistance, solvent resistance, and acid resistance were evaluated based on the standards of 28 days after age.

Appearance: The surface of the cured product molded according to JIS A1108 was visually evaluated using the following criteria.

○: The surface of the cured product is glossy and smooth.

Δ: The gloss of the surface of the cured product is slightly inferior.

X: The surface of the cured product lacks smoothness.

Bending strength: Measured according to JIS A1106.

Compressive strength: Measured according to JIS A1108.

Abrasion resistance 2 Using the above mortar composition, 50mmφX
The cured product was prepared to have a cylindrical shape of 50 mm, and the material was aged 2.
After 8 days, this cured product was placed on a 10-mesh fly and shaken for 2 minutes using a rotary tube shaking method (manufactured by Teiko Seisakusho), and the abrasion resistance was evaluated using the following formula.

A; Weight before shaking (g) B: Weight after shaking (g) Water resistance, seawater resistance, solvent resistance: Used to measure compressive strength after 28 days of age Equivalent specimens were treated with deionized water, seawater, Soaked in benzene for 28 days, Evaluated based on standard.

O: The mortar surface has the same gloss as the specimen before immersion.

△　; Mortar surface has no gloss X: Mortar surface is whitened.

Acid resistance: The same specimen used to measure the compressive strength after 28 days of age was immersed in a 1 weight 2 hydrochloric acid aqueous solution for 28 days, and evaluated according to the following criteria.

○: The surface of the specimen is slightly whitened compared to the specimen before immersion, but there is no change in shape at all.

△: There is whitening on the surface of the specimen, and the surface of the shape is slightly eroded.

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

The properties of the aqueous emulsion thus obtained and the performance of the mortar composition are shown in Tables 1 and 2.

Samples Nα1.2.3 and 4 are examples of the present invention, and are found to have extremely good strength (compressive strength, bending strength) and water resistance. Note that samples Nα5.6 and A-D are comparative examples.

Sample Nα A; EVA D; Aqueous emulsion-free Example 2 Stearyl 2-hydroxy-
Sodium 3-allyloxy-1-propyl succinate succinate, (b) Sodium branched alkylbenzene sulfonate having 10 to 14 carbon atoms/sodium xylene sulfonate = 98/2 weight ratio, (c) Polyoxypropylene polyoxy Ethylene P, P'-isopropylidene diphenyl ether diacrylate ester # (POP=
2, EOIs=18) Milk and other agents L,,7'7'J#
Example 1 Using 156 parts by weight of an unsaturated monomer mixture consisting of 90 parts by weight of acid-T-tyl, 60 parts by weight of methyl methacrylate, 4.5 parts by weight of N-methylolacrylamide, and 5 parts by weight of water. Emulsion polymerization was carried out in the same manner as in 1 to prepare an aqueous emulsion.

Properties of the aqueous emulsion thus obtained and 2.
It was air-dried at 5° C., and the properties of the formed film and its performance as a compounding agent for hydraulic inorganic materials were measured and evaluated in the same manner as in Example 1. The results are shown in Table-3 and Table-4.

Samples Nos. 8, 9, 12, and 13 are examples of the present invention, and samples Nos. 7, 10, 11, and 14 are comparative examples.

The following unsaturated monomer mixtures T1 and T2 were prepared at a material temperature of 30°C (PO[' = 8.3, EOP = 5.7) and emulsion polymerization was carried out according to Ethyl Example 1. , an aqueous emulsion was prepared. Properties of the obtained aqueous emulsion and temperature at 30°C
The characteristics of the film formed by air-drying and the performance as a hydraulic inorganic material molded article were measured and evaluated according to Example 1.

The results are shown in Table-5 and Table-6.

Samples Nα15 and 16 are examples of the present invention.

Table-6 Example 4 Sample No. of Examples 1, 2 and 3, 1, 3, 8,
75% by weight (6.0 parts by weight) of the emulsifier composition of Nos. 12 and 15 and polyoxyethylene nonylphenyl ether (EO
'P=14) 2.0 parts by weight was used as the emulsifier composition (8.0 parts by weight), and an aqueous emulsion was prepared according to Examples 1, 2, and 3 corresponding to sample Nα.

Furthermore, using these aqueous emulsions, the following polymer cement mortar was prepared and used as a polymer cement mortar for finishing the exterior walls of reinforced concrete building structures from which the formwork had been removed.
0) or yarn tube finishing agent (flow value 18
0) was evaluated.

Re: Tanami Mizuse Mining Co., Ltd. Diamond Silica Sand 112: Asenocement manufactured by Nippon Cement ■ (Portland cement The results are shown in Tables 7 and 8. Samples Nα17~
21 is an example of the present invention.

Moreover, from samples Nα17 to 21 (Table 8), it can be seen that the compounding agent for hydraulic inorganic materials of the present invention is also optimal as a compounding agent for polymer cement mortar.

The performance of polymer cement mortar was measured and evaluated using the following method.

$1: Amount of clumps $2 = Thick coating The thickness of the polymer cement mortar without sag was measured when spraying or thread finishing the polymer cement mortar on the outer wall of a reinforced concrete building structure.

*3: Polymer bleed out IQ the polymer cement mortar immediately after adjustment.

After 500 g of the polymer was placed in a beaker and allowed to stand for 10 minutes, the presence or absence of polymer bleed in the upper layer of the polymer cement mortar was visually determined.

114 = Aesthetic appearance The external wall was sprayed with polymer cement mortar or finished with yarn tubes, and was visually judged after 28 days.

95: Water resistance Immediately after the preparation, 250 g of polymer cement mortar was uniformly filled into a 150 mΩ desposable cup (pp) manufactured by Iuchi Seieido Co., Ltd. to prevent air from entering.

Next, after standing for 2 days, the formwork was cut out, and after being left standing at room temperature for another 26 days (material age), this cured body was immersed in a 500 m Q beaker filled with tap water at 25 ° C.
The time required for the surface of the cured product to whiten or swell was measured.

11 ['=Abrasion resistance 50mmφX A cured polymer cement mortar was prepared to have a cylindrical shape of 50 mm. After 28 days, the cured polymer cement mortar was placed on a 10-mesh sieve, and the rotary tube was shaken. Shaking was carried out for 2 minutes using the method (manufactured by Teiko Seisakusho), and the abrasion resistance was evaluated using the following formula.

A: Weight before shaking (g) B: Weight after shaking (g) Example 5 The table below shows the fine hollow glass spheres obtained from calcined gypsum and whitebait.
9 and mixed uniformly to obtain a gypsum board material. Next, take the minimum amount of water that can completely turn this gypsum board material into a slurry, and in this water, add a compound (water repellent) represented by the chemical formula [C,7H33CONHCH2-CH◎]CQ0, and the sample Nα1 of Example 1. and the aqueous emulsion were added according to the proportions shown in Table 9 and mixed uniformly. Then, after adding the gypsum board material to this mixture and mixing it uniformly, a 150 mm x 180
It was molded into a boat of mm x 9 mm, and dehydrated and dried at 80°C until it reached a constant weight. The thus obtained board was used as a test board, and its resistance strength, compressive strength, and water resistance (water absorption rate) were measured, and the results shown in Table 9 were obtained.

In addition, for comparison, test boards were created by changing the proportions of calcined gypsum and fine hollow glass spheres obtained from shirasu, or the amounts of the water repellent and the aqueous emulsion.
Similarly, water absorption, bending strength, water resistance, water absorption, and appearance were measured.

The water absorption rate was measured by immersing the test board in water at 30° C. to absorb water, and determining the water absorption rate from the amount of water absorbed 24 hours later according to the following formula.

In addition, the measurement of bending strength and compressive strength is based on JIS K-7.
203 and JIS K-6911.

Table 8 shows the performance of the gypsum board thus obtained. Samples Nα26 to 33 are examples of the present invention, and samples Nα34 to 38 are comparative examples.

Example 6 The dispersion stability of the aqueous emulsions of Sample Nos. 1 to 16 was evaluated in the following manner. The results are shown in Table-10. The dispersion stability test was conducted as follows.

[Dispersion stability]

Aqueous emulsion 1 with solid concentration adjusted to 40% by weight 2
After putting 50g in a 220m Q glass bottle and sealing it, it was left in a constant temperature room at 25°C for 6 months and in a constant temperature room at 45°C for one week, and the appearance, transmittance, viscosity and average particle size were measured. The dispersion stability of the aqueous emulsion was evaluated. The appearance, transmittance, viscosity, and average particle diameter were measured by the following methods.

Appearance: Evaluated by visual judgment at 25°C according to the following criteria.

0; Transparent or translucent liquid Δ; Cloudy liquid The absorbance under 800 nm light irradiation was determined, and the light transmittance (%) was calculated.

Viscosity The viscosity at 25° C. was measured using a Nibruckfield viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.).

Average particle size: Coulter Submicron Particle Analyzer (Coaltar Electronics, Inc., USA, Cou
The average particle diameter was measured using the following method (Model NJ).

In addition, the aqueous emulsions of samples 1 to 4.8, 9, 12.13 and 15 to 16, which were subjected to the strong heating dispersion stability test and left in a constant temperature room at 45°C for one week, were prepared according to Example 1. A film was formed, and the film properties and performance as a compounding agent for hydraulic inorganic materials were measured according to Example 1. Transparency, water resistance,
Evaluations of adhesive, solvent resistance (crosslinking), mechanical strength, and compounding agent for hydraulic inorganic materials were conducted in Examples 1 and 2.
Good results almost the same as those of 3 and 3 were obtained.

The changes in particle size distribution before and after the static stability test are shown in graphs as shown in FIGS. 1(A) and 1(B).

In addition, sample No. 5 in Table 1 had a lot of extra large particles and could not be measured due to poor dispersion after being left standing for one week at 45°C. Therefore, both sample No. 1 and sample No.
The changes in particle size distribution after standing for several months were illustrated and compared.

In addition, Example 1 (sample Nα1) and Example 1 (sample Nα
After the aqueous emulsion in 5) was allowed to stand at 25° C. for 6 months, changes in low-boiling components in the aqueous emulsion were analyzed using a gas chromatograph under the following conditions.

The results are shown in FIG. 2(A) and FIG. 2(B).

Carrier gas: N220+naQ/min temperature increase conditions:
In1tia1160℃Fjnal 230'C Temperature rising rate 5℃/min Ho1d Time 10 minutes FID sensitivity: 104MΩ

[Brief explanation of the drawing]

Figure 1 (A) and Figure 1 (B) show the change in particle size distribution of the aqueous emulsion of the present invention product (sample No. 1) and comparative product (sample Nα5) after standing at 25°C for 6 months, respectively. This is a graph representing Figure 2 (A) and Figure 2 (B) respectively show the product of the present invention (sample N).
It is a graph showing changes in low boiling point components in aqueous emulsions of α1) and a comparative product (sample Nα5) after they were allowed to stand at 25° C. for 6 months. The peaks in FIG. 2(A) and FIG. 2(B) are as follows. ■ is the peak of the solvent methanol, ■ is the peak of the raw material monomers ethyl acrylate and methyl methacrylate, and ■ is derived from the emulsifier polyoxyethylene-p,p'-isopropylidene diphenyl ether (EOP=20) dimethacrylate ester. The peaks 1, 2, 2, 2, and 2 are peaks due to low-boiling components that are not derived from the raw materials. Recommendation to the Sea of Kyosugae Station ℃- Detention; Survival - Hebo Tokogama ℃- Proceedings Amendment Written by the Commissioner of the Patent Office on September 78, 1986 1) Mr. Moon Tsuyoshi ■, Incident Indication of Patent Application No. 323275 of 1988 2, Name of the invention Compounding agent for hydraulic inorganic materials 3, Relationship with the case of the person making the amendment Patent applicant 1,) Number of inventions increased by the amendment 07, Column 8 of "Detailed Description of the Invention" of the specification to be amended, contents of the amendment The following amendments will be made to the specification of the present application. (1) Page 4, line 7: “Because it has thixotropic properties,
” has been corrected to “J, as it is a fine particle.” (2) “In good condition” on page 4, line 9 has been changed to “In good condition.”
No bleed-out of aqueous emulsions. ” will be corrected. (3) Change “1 to 20” in the third line from the bottom of page 14 to “0 to
Corrected to 20. (4) General formula (XI) in the first line of page 20 is corrected as follows. (5) “R14, RtsJ” in the 9th line from the bottom of page 20,
"R□4, Rxs, LsJ." Corrected to ``ethylene (polyoxypropylene) dialkyl phenyl ether.'' (7) Correct "Fly" in the fourth line from the bottom of page 36 to "Furui". (8) “Table 8” on page 49 will be corrected as shown in the attached sheet. (9) "Tal Double Beer" at the end of page 55 has been corrected to "Tal Double Beam."

Claims (1)

[Claims] (1) The average particle size is 100 nm or less, has a crosslinked structure, has a glass transition temperature higher than the value calculated by the weight fraction method, and has a zeta potential of -30 mV or less,
A compounding agent for hydraulic inorganic materials characterized by containing as an essential ingredient an aqueous emulsion with excellent dispersion stability over a long period of time.