JP2568420B2 - Compounding agent for hydraulic inorganic materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a formulation for a hydraulic inorganic material containing an aqueous emulsion as a main component.

(Prior art)

Conventionally, its mechanical strength, such as adhesive strength, waterproofness, chemical resistance, bending strength, tensile strength, etc., or abrasion resistance to hydraulic inorganic compositions such as cement paste, mortar, gypsum, concrete, grout, etc. Many proposals have been made to add various compounding agents in order to improve the appearance and the like of these molded articles and 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 and JP-A-58-49653 disclose styrene / vinyl chloride / ethylene three-dimensional polymer emulsion, ethylene-acetic acid for a hydraulic inorganic composition such as mortar and cement. It is disclosed that various polymer compounds such as a combination of a polymer emulsion such as a vinyl copolymer emulsion, a synthetic rubber latex such as styrene-butadiene and styrene-butadiene-methyl methacrylate, and 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 properties and the like have not yet been sufficiently satisfied.

〔Purpose〕

An object of the present invention is to provide excellent dispersion stability over a long period of time, and, unlike the conventional compounding agents, to have excellent miscibility (impregnation) with a hydraulic inorganic material, and to enhance the appearance of a cured hydraulic inorganic material. An object of the present invention is to provide a compounding agent for a hydraulic inorganic material which can further improve various properties such as water resistance, solvent resistance, and mechanical properties.

〔Constitution〕

According to the present invention, the average particle diameter is 100 nm or less, has a crosslinked structure, has a high glass transition temperature by a value calculated by the weight fraction method, the zeta potential is -30 nv or less, dispersion stable The present invention provides a compounding agent for a hydraulic inorganic material, which comprises an aqueous emulsion having excellent properties over a long period of time as an essential component.

The aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic material of the present invention, first has an average particle diameter of 100 nm.
In the following, the thickness is preferably 80 nm or less.

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 100 nm or less as described above. Since it is preferably limited to 80 nm or less, the immersion property to a hydraulic inorganic material is good, and various properties such as heat sealing, transparency, smoothness, and glossiness of a coating and a cured inorganic material are greatly improved. It is possible to improve. In addition, since they are fine particles, the adhesion between the hydraulic inorganic material and the aqueous emulsion of the present invention is good, but there is no bleed out of the aqueous emulsion.

If the average particle size exceeds 100 nm, the adhesiveness (density) at the time of forming a film is inferior, and the gloss, transparency and smoothness of the film and the inorganic cured product may be lacking, or an aqueous emulsion may be formed. However, the intended purpose of the present invention cannot be achieved because of poor permeability with the hydraulic inorganic material of Example 1 and bleed-out of the aqueous emulsion.

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

That is, the aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic material of the present invention, is characterized in that the inside and / or between the particles are, for example, the functional groups of the raw material unsaturated monomers or the functional groups having these and an emulsifier. Since the group is cross-linked by ionic bonding, hydrogen bonding, condensation reaction or assembly reaction, a film having excellent transparency, tackiness, water resistance, solvent resistance and mechanical strength can be formed.

Further, the third feature of the aqueous emulsion, which is an essential component of the hydraulic inorganic material-soluble compounding agent of the present invention, is that it has a higher glass transition temperature than the value calculated by the weight fraction method.

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

W _A ; weight fraction of component A W _B ; weight fraction of component B Tg _A ; glass transition temperature of component A Tg _BB ; glass transition temperature of component B This glass transition temperature is affected by various structural factors, In general, it is known that the glass transition temperature of a polymer having a crosslinked structure increases, and that the addition of a polymer plasticizer lowers the glass transition temperature.

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

The aqueous emulsion of the present invention has a film-forming ability exhibiting a glass transition temperature higher than the value calculated by the weight fraction method as described above, and has a dense cross-linked structure, so that it is transparent, tacky, and smooth. Excellent in water resistance and solvent resistance,
Furthermore, since it is possible to form a film that is hard and has good mechanical strength such as tensile strength and mojoras strength, the transparency, smoothness, water resistance, chemical resistance, and abrasion resistance of a cured body of a hydraulic inorganic material can be improved. The mechanical strength such as the property can be improved.

The fourth feature of the aqueous emulsion, which is an essential component of the compounding agent for hydraulic inorganic material of the present invention, is as follows:
It has a value of -30 mV or less, preferably -50 mV or less.

Generally, dispersed colloidal particles such as an aqueous emulsion have an electrokinetic potential (zeta potential) in a system surrounding the particles at the interface between the particles and the solution. When the zeta potential is negatively charged, it is necessary that the zeta potential is lower, but the polymer latex of the present invention has a zeta potential of -30 mV or less, preferably-as described above. Since having a value of 50 mV or less, the colloid particles in the dispersion show very high stability.

The fifth feature of the aqueous emulsion, which is essential for the formulation example for hydraulic inorganic material 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 diameter.
Although it is a thing of 100 nm or less, even if this thing is subjected to a forced heating dispersion stability test at 45 ° C. for one week, the average particle diameter does not substantially change, even if there is a change,
Usually, the average particle size shows a particle size distribution of one peak distribution of a particle distribution of 150 nm or less, and even when the rate of change is large,
97 particles with an average particle size less than 150 nm
% Or more, and the second peak due to agglomeration of particles has a particle size distribution of 300 nm or more, indicating a two-peak distribution of 3% or less,
The particle size distribution of the average particle size is extremely small.

Further, the aqueous emulsion which is an essential component of the compounding agent for hydraulic inorganic material of the present invention, even when subjected to a long-term dispersion stability test at 25 ° C. for 6 months, is apparent from Examples and Comparative Examples described later. In addition, the rate of change of the average particle diameter is extremely small.

Therefore, the aqueous emulsion according to the present invention is substantially free of coalescence and aggregation of particles even with the lapse of time, and does not generate coarse particles. Since there is no change in viscosity and no change in appearance, the composition exhibits excellent dispersion stability over a long period of time, and when a film is formed, the mechanical strength does not decrease due to the formation of coarse particles.

The reason why the aqueous emulsion, which is an essential component of the hydraulic inorganic material compounding agent of the present invention, exhibits excellent dispersion stability as described above is not necessarily clear, but since the average particle diameter is 100 nm or less, Undesirable side reactions such as a polymerization reaction and a cross-linking reaction which are caused by the polymerizable or reactive emulsifier remaining in the system are relatively active in the Brownian motion between the particles, and in the present invention, the sulfonate type emulsifier and The reactive emulsifier is present in a regular and well-ordered manner. Furthermore, as will be apparent from the following drawings, in the course of emulsion polymerization, low-molecular (low-boiling) compounds excluding unsaturated monomers used as raw materials and (Or) less by-products of low-boiling compounds, which are thought to promote coalescence and aggregation of the particles, prevent side reactions such as polymerization reaction and cross-linking reaction. The reason, because each particle is sufficiently protected, blocked coalescence or aggregation of particles, that it does not promote the formation of coarse particles is estimated that basic factors.

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

In addition, the average molecular weight of the aqueous emulsion, which is an essential component of the hydraulic inorganic material compounding agent of the present invention, is generally several hundred thousand or more, often about several tens of millions to several hundred millions, and has a high degree of crosslinking. In some cases, the molecular weight may be as high as tens of millions to 1 billion or more.

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

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

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 methylstyrene and chlorostyrene, vinyl chlorides such as vinyl chloride and vinyl bromide, vinylidene chloride,
Examples thereof include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, vinylidenes such as vinylidene bromide, dienes such as butadiene, chloroprene and isoprene, and vinyl pyridine. Examples thereof include (meth) acrylates and lower fatty acids. The use of 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 within and / or between the particles of the aqueous emulsion to be formed, 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) to (VII). 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 , 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, the number from 1 to 3 alkyl group carbon atoms, a carboxyl group, Or -CONHCONH ₂ E; 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) Glycidyl acrylate Glycidyl methacrylate Glycidyl crotonate Glycidyl allyl ether Examples of general formula (III) Hydroxyethyl acrylate Hydroxyethyl methacrylate Hydroxyethyl crotonate Hydroxypropyl acrylate Hydroxypropyl methacrylate Hydroxypropyl crotonate Hydroxybutyl acrylate Hydroxybutyl Methacrylate polyoxyethylene monoacrylate polyoxyethylene monomethacrylate polyoxyethylene monotonate polyoxypropylene monoacrylate polyoxypropylene monomethacrylate polyoxypropylene monotonate polyoxybutylene monoacrylate polyoxybutylene monotonate hydroxye Luaryl 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 Examples of (V) Acrylamide Methacrylamide Aminopropylmethacrylamide Monomethylacrylamide Monoethylacrylamide Diethylolaminopropylacrylamide Example of the general formula (VI) Acrylic acid Methacrylic acid Crotonic acid Itaconic acid Maleic acid and its alkyl group having 1 to 5 carbon atoms Monoester or anhydride Fumaric acid and its monoester or anhydride of alkyl group having 1 to 5 carbon atoms Alanide maleate Alanide malate 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 usage ratio of the unsaturated monomer having a reactive functional group to the monomer is from 99/1 to 60/40 (weight), and preferably from 99/1 to 90/10 (weight). This usage rate is 99/1
If it is larger than the particle size of the aqueous emulsion to be formed and the cross-linking between the particles becomes smaller, and if it is smaller than 60/40, the emulsion copolymer lacks a large amount of aggregates or the film is poorly formed. In some cases, cracks or streaks may occur.

In the present invention, the following general formulas (IX), (X), (XI) and
At least one reactive emulsifier represented by (XII), (XIII) or (XIV), a sulfonate-type emulsifier represented by the general formula (XV), and a polyoxyalkyleneethylenically unsaturated carboxylic acid represented by the general formula (XVI) Acid polyesters (hereinafter abbreviated as poly (meth) acryloyl paint emulsifier)
It is necessary to use an anionic emulsifier consisting of at least three components.

(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, 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 A preferable real number is 8 or more moles of the added alkylene oxide in the molecule M; monovalent or divalent cation m; ionic valence of M Or _{-O-C n H 2n -g 2} (R 18) g 2 -O- R 16, R 17; hydrogen or carbon atoms 1-2 alkyl group R _18; hydrogen or R ₁₀ Oa ₅ H or g ₁ ; 0 to 5 integers g ₂ ; 0 to 10 integers n; 1 to 10 integers a ₅ ; 1 to 50 real numbers And y is a real number of 1 to 5 R ₁₉ , R ₂₀ ; hydrogen or an alkyl group having 1 to 20 carbon atoms Y ′; an alkylene group having 3 to 8 carbon atoms, oxygen or a carbonyl group) Ultrafine particles with a fine cross-linked structure inside and / or between particles, forming a film with a glass transition temperature higher than the value obtained from the calculation formula, and a zeta potential of -30 mV or less In order to obtain an ultrafine crosslinked aqueous emulsion having excellent dispersion stability in which coalescence and aggregation of particles are suppressed over a long period of time, an emulsifier used in the emulsion polymerization of the unsaturated monomer (a ) The above general formulas (IX), (X), (XI), (XI
At least one of the reactive emulsifiers represented by I), (XIII) and (XIV), (b) a sulfonate type emulsifier represented by the general formula (XV), and (c) a compound represented by the above general formula (XVI) (A) / (c) = 9/1 to 1/9 weight ratio, preferably 4/1 to 1/4 weight ratio, (b) / (A) + (c) = 7/3 to 1/9
It is used in a weight ratio, preferably 3/2 to 1/4 by weight.

If the usage ratio of (a) / (c) is larger than 9/1,
The resulting aqueous emulsion may have poor crosslinkability and / or dispersion stability, and if it is smaller than 1/9, a large amount of aggregates may be formed during emulsion polymerization or the average particle size of the resulting aqueous emulsion may be large. There is.

On the other hand, when the use ratio of (b) / (a) + (c) is more than 7/3, the inside of the resulting aqueous emulsion particles and / or
Or, the degree of cross-linking between particles is small, and the formed film is inferior in transparency, water resistance and solvent resistance. If it is smaller than 1/9, it lacks microemulsification or solubilization of unsaturated monomers, and an aqueous emulsion formed Or the average particle size of
Even if the particles coalesce and agglomerate and become cloudy with the progress of emulsion polymerization, or even if an aqueous emulsion of transparent or translucent ultrafine particles is formed, the zeta potential is negatively small and stored for a long period of time. As a result, simultaneous coalescence and aggregation of the particles easily occur, coarse particles are formed, the cloudiness becomes remarkable, the aqueous emulsion undergoes layer separation, or the viscosity is significantly increased.

By using these emulsifiers in the above ratio, they are ultrafine particles, have a crosslinked structure, exhibit a glass transition temperature higher than the value calculated by the weight fraction method, and have a high negative zeta potential, and furthermore, An aqueous emulsion excellent in dispersion stability in which coalescence and aggregation of particles are suppressed over a long period of time can be produced.

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.

Known anionic, nonionic and cationic surfactants may be added as necessary. Specific examples thereof include higher alcohols, higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts and styrenated. The fourth of each of a phenol alkylene oxide adduct, a sulfate type, an olefin sulfonate type such as an α-olefin, a long chain alkylamine alkylene oxide adduct and a dilong chain alkylamine alkylene oxide adduct
Ammonium salt type, N- (1,2-dicarboxyethyl)
Sodium salt of N-octadecylsulfonic acid monoamide, dialkyl sulfosuccinate, bleached ceramic resin, organic and inorganic salts of 4-hydroxy-4,5-dicarboxypentadecanoic acid or 4,5-dicarboxy-pentadecanoroid, etc. Is exemplified.

In particular, when an aggregate (dama) is formed between a hydraulic inorganic material (cement, gypsum, etc.) and an aqueous emulsion of the present invention, the above polyoxyethylene (polyoxypropylene) dialkyl phenyl ether, Mixing a nonionic surfactant such as polyoxyethylene (polyoxypropylene) alkyl ether or polyoxypropylene ethylene glycol with the emulsifier compositions of (a), (b) and (c) above is effective in suppressing lumps. .

In order to obtain an aqueous emulsion which is a compounding agent for hydraulic inorganic material of the present invention, a conventionally known emulsion polymerization method can be used as it is in the presence of the unsaturated monomer and the emulsifier. For example, for unsaturated monomers
The polymer of the unsaturated monomer may be emulsified and dispersed in water at a concentration of 10 to 60% by weight in the presence of a polymerization initiator corresponding to 0.1 to 5% by weight to perform emulsion polymerization.

As the polymerization initiator, a water-soluble single initiator or a water-soluble redox dispersing agent used for ordinary emulsion polymerization is used, such as hydrogen peroxide alone or hydrogen peroxide and tartaric acid, citric acid, In addition to combinations with carboxylic acids such as ascorbic acid, and combinations of hydrogen peroxide with oxalic acid, sulfinic acid and their salts or oxyaldehydes, water-soluble iron salts, etc., as well as persulfates, percarbonates and peroxides Peroxides such as borates, 2,2'-azobis (2-amidinopropane) and its salts, 2,2'azobis (N, N'-dimethylene-isobutylamidine) and its salts, 4,4'- Water-soluble azo diameter initiators such as azobis (4-cyanovaleric acid) and salts thereof 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 dissolving the hydraulic inorganic material of the present invention.

In addition, a water-soluble nonionic polymer substance, an anionic polymer substance, and, if necessary, a cationic polymer substance can be used in combination. Further, a plasticizer and a pH adjuster usually used in the conventional method can be used together if necessary.

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 include polymers such as anionized hydroxyethylcellulose, anionized starch, anionized guar gum, anionized chitosan, carboxymethylcellulose, and anionized polyvinyl alcohol.

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 high-molecular substances, anionic high-molecular substances and cationic high-molecular substances to be used in combination as needed can be used alone or in combination of two or more.
The addition amount is suitably 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on the monomer to be subjected to emulsion polymerization.

Further, phthalic acid esters, phosphoric acid esters and the like can be used as the plasticizer. Further, salts such as sodium carbonate, sodium bicarbonate and sodium acetate are used as pH adjusters.
It can be used in the range of 01 to 3% by weight.

In order to obtain a hydraulic inorganic material by 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, gypsum, concrete, grout, etc. The auxiliary additives may be mixed and then cured by known means.

Auxiliary additives used in the present invention include a color pigment and a high strength agent, a dispersant, a waterproofing agent, an antifoaming agent, an anti-linking agent,
Examples include preservatives, conductive (antistatic) agents, and strengthening agents.

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

In addition, calcium chloride or the like is used as an early-strength agent, ligninsulfonate or oxycarboxylate is used as a dispersant, calcium stearate or the like is used as a waterproofing agent, and tributyl phosphate or poly is used as an antifoaming agent. Oxyalkylene glycols, polyoxyalkylene alkyl ethers and polyoxyalkylene (di) alkyl phenyl ethers; nitrogen-containing sulfur compounds as antifreeze agents; and conductive (antistatic) agents such as iron powder and copper powder. Gold powder or carbo black can be used, and as a reinforcing agent, carbon fiber, glass fiber, synthetic resin fiber, or the like can be used.

〔effect〕

The compounding agent for hydraulic inorganic material of the present invention has an average particle diameter of
100 nm or less, having a cross-linked structure, having a glass transition temperature higher than the value calculated by the weight fraction method, because the dispersion stable number was excellent over a long period of time and an aqueous emulsion as an essential component, Unlike conventional compounding agents for hydraulic inorganic materials,
It can enhance the beauty of the cured body of hydraulic inorganic material,
Since various properties such as water resistance, solvent resistance, and mechanical strength such as bending strength, compression strength, and abrasion resistance can be further improved, the practical value thereof is extremely high.

Accordingly, the hydraulic inorganic material composition such as polymer cement mortar (concrete) and gypsum using the hydraulic inorganic material compounding agent of the present invention can be used as an exterior (repair) material for building foreign matter, a tiled adhesive, a warehouse, a passage, etc. , Livestock farms,
Floor materials for gas stations, etc., anticorrosion linings for floors of ALC steel bars, corrosion protection linings for water storage tanks, pools, silos, tennis courts, etc., deck covering materials for ship decks, bridge decks, etc., acid-resistant fume pipes, GRC products Etc., specially molded concrete products, bus terminals, semi-rigid roads in tunnels, spray protection coating materials for concrete skeletons, color conductive coating materials, electromagnetic wave shielding materials, super-strength molded products, heavy-duty corrosion-resistant coating materials, mortar floating repair, slope It is excellent as a coating material for grouting materials such as a cable-stayed wire, a decorative bottle, a tile, and a decorative molded article such as an interlocking.

〔Example〕

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

Example 1 8 parts by weight of the emulsifier shown in Table 1 and 150 parts by weight of water were charged and dissolved in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction pipe, and a dropping funnel. The atmosphere was replaced with nitrogen gas. Separately, 90 parts by weight of ethyl acrylate, 60 parts by weight of methyl methacrylate, 156 parts by weight of an unsaturated monomer mixture consisting of 4.5 parts by weight of N-methylol acrylamide and 1.5 parts by weight of water, and 15 parts by weight of The mixture was added to the reaction vessel and emulsified at 40 ° C. for 30 minutes. Then, after the temperature was raised to 60 ° C., the polymerization initiator 2,2′-azobis (N, N′-dimethyleneisobutylamidine) hydrochloride was added to 9.0 × 10 ⁻³ mole /
It is dissolved in 48.5 parts by weight of water so as to become an aqueous phase l, added to the reaction vessel, and immediately the remaining unsaturated monomer is immediately dropped continuously into the reaction vessel over 30 minutes, and polymerized at 60 ° C. Was done. After completion of the dropwise addition of the unsaturated monomer, the mixture was aged at 60 ° C. for 60 minutes.

(Evaluation of aqueous emulsion)

The average particle size, 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, USA, Coulter
(Model N4 type).

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

；: 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.

Zeta potential; Laser rotating prism type colloid particle zeta potential measurement device (LASER ZEETM M manufactured by PEN KEN INC, USA)
odel 500).

Film-forming property; air-dried at 25 ° C. to form a film, and the state of the formed film was visually evaluated.

；: A smooth and uniform film is formed.

Δ: A film having a network streak is formed.

X: No film is formed.

Glass transition temperature (Tg) Thermal diffraction analyzer (SSC 5000, manufactured by Seiko Denshi Kogyo Co., Ltd.)
Tg was measured using DSC 200). The calculated Tg was calculated by the weight fraction method (described above).

[Evaluation of film properties]

The above aqueous emulsion 30 having a solid content adjusted to 20% by weight.
Weight part is evenly cast on a glass plate of 12cm x 14cm, 25 ℃
The film was air-dried to form a film, and the aging of the film was evaluated. The film characteristics were evaluated according to the following criteria.

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

Water resistance: The film was cut into a size of 2 cm × 4 cm, immersed in a petri dish filled with water at 20 ° C., and the time until the film became white was judged visually.

;: 10 days or more Δ; 2 days or more, less than 10 days ×; less than 2 days Adhesion: The film surface was touched with fingers, and the solid feeling was evaluated according to the following criteria.

○: No stickiness △: Slightly sticky ×: Sticky Elongation and strength: Dumbbells were prepared in accordance with JIS K-6681, tensile strength at break, elongation and 50%, 100% and 200% modulus. Was measured.

(Preparation and performance evaluation of hydraulic inorganic material)

According to JIS A6204 (1982), Nippon Cement Co., Ltd. Asano Cement 475Kg / m ³ , fine aggregate (specific gravity: 2.64, crushing rate:
2.42) 950 kg / m ³ , an aqueous emulsion with an addition amount of 20% by weight and a mortar composition obtained by adding water so that the flow value becomes 140 ± 5 at 25 ° C. after 28 days of material age, appearance according to the following criteria,
The bending strength, compression strength, abrasion resistance, water resistance, seawater resistance, solvent resistance and acid resistance were evaluated.

Appearance: The surface of the hardened material shaped according to JIS A1108 was visually judged according to the following criteria.

；: The cured product surface is glossy and smooth.

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

X: The smoothness of the cured body surface is lacking.

Flexural strength: Measured according to JIS A1106.

Compressive strength: Measured according to JIS A1108.

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) Water resistance, seawater resistance, solvent resistance: Deionize equivalent specimens used for measuring compressive strength after 28 days of material age It was immersed in water, seawater, and benzene for 28 days and evaluated according to the following criteria.

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

Δ: no gloss on mortar surface ×: white mortar surface

Acid resistance: Equivalent specimens used for measurement of compressive strength after 28 days of aging were immersed in a 1% by weight aqueous hydrochloric 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.

The properties of the aqueous emulsion thus obtained and the performance of the mortar composition are shown in Tables 1 and 2. Sample N
o. 1, 2, 3 and 4 are examples of the present invention, and it can be seen that the strength (compression strength, bending strength) and water resistance are remarkably good. Samples Nos. 5, 6 and A to D are comparative examples.

Example 2 (a) Sodium stearyl 2-hydroxy-3-allyloxy-1-propyl succinate sulfonate, (b) Sodium branched chain alkylbenzene sulfonate having 10 to 14 carbon atoms / xylene as shown in Table 3. Sodium sulfonate = 98/2 weight ratio, (c) polyoxypropylene polyoxyethylene P, P'-isopropylidene diphenyl ether diacrylate (PO = 2, EO =
Using 18) as an emulsifier, 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. Emulsion polymerization was carried out in the same manner as in Example 1 to prepare an aqueous emulsion.

Properties of the aqueous emulsion thus obtained and
The properties of the film which was air-dried at 25 ° C. and formed and the 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 Tables 3 and 4.

Samples No. 8, 9, 12, and 13 are examples of the present invention,
7, 10, 11 and 14 are comparative examples.

Example 4 The following emulsifiers E-1 and E-2 shown in Table 5, and By adjusting the unsaturated monomer mixture M-1 and M2 shown below, Emulsion polymerization was carried out according to Example 1 to prepare an aqueous emulsion. The properties of the obtained aqueous emulsion, the characteristics of a film formed by air drying at 30 ° C., and the performance as a molded product of a hydraulic inorganic material were measured and evaluated in accordance with Example 1. The results are shown in Table-5 and Table-6. Sample Nos. 15 and 16 are examples of the present invention.

Example 4 75% by weight (6.0 parts by weight) of the emulsifier composition of Sample Nos. 1, 3, 8, 12 and 15 of Examples 1, 2 and 3 and 2.0 parts by weight of polyoxyethylene nonylphenyl ether (EO = 14) Aqueous emulsion was prepared according to Examples 1, 2 and 3 corresponding to Sample No., using the same parts as the emulsifier composition (8.0 parts by weight).

Further, using these aqueous emulsions, the following polymer cement mortar was prepared, and used as a spray finish (flow value 23) as a polymer cement mortar for finishing an outer wall of a reinforced concrete building structure from which a mold was removed.
0) or left tube finish (using a flow value of 180) was evaluated.

The results are shown in Tables 7 and 8. Sample Nos. 17 to 21 are examples of the present invention.

Sample Nos. 17 to 21 (Table 8) show that the compounding agent for hydraulic inorganic materials of the present invention is also optimal as a compounding agent for polymer cement mortar.

In addition, the performance evaluation of the polymer cement mortar was measured and evaluated by the following method. ^{* 1} : Lama amount ^{* 2} : Thick coating properties The thickness of the outer wall of a reinforced concrete building structure was measured when the polymer cement mortar was sprayed or left-tube finished without sagging in the polymer cement mortar. ^{* 3} : Bleed-out of polymer 500 g of the polymer cement mortar immediately after the adjustment was placed in one beaker, allowed to stand for 10 minutes, and visually determined whether or not polymer bleed was present in the upper layer of the polymer cement mortar. ^{* 4} : Aesthetics The outer wall after spraying polymer cement mortar or finishing the left tube was visually judged 28 days after the material age. ^{* 5} : Water resistance 250 g of polymer cement mortar immediately after preparation is uniformly filled in a 150 ml desporable cup (PP) manufactured by Inuchi Seieido Co., Ltd. so that air does not enter.

Next, after leaving still for 2 days, the mold was cut out, and left still at room temperature for 26 days (material age). Then, this cured product was immersed in a 500 ml beaker filled with 25 ° C tap water and cured. The time until the body surface was whitened or swollen was measured. ^{* 6} : Abrasion resistance A cured body of polymer cement mortar was prepared so as to have a cylindrical shape of 50 mmφ x 50 mm. After 28 days of age, the cured body of polymer cement mortar was placed on a 10-mesh sieve, and a low tap vibration was applied. It is 2 by Toho method (manufactured by Heiko Works)
After shaking for a minute, the abrasion resistance was evaluated by the following equation.

A: Weight before shaking (g) B: Weight after shaking (g) Example 5 Gypsum and fine hollow glass spheres obtained from shirasu were blended according to the ratio shown in Table 9 and uniformly mixed. Gypsum board material was obtained. Next, take the minimum amount of water that allows the gypsum board material to completely slurry, and add the chemical formula into the water. (Water repellent) and the aqueous emulsion of Sample No. 1 of Example 1 were added according to the proportions shown in Table 9 and uniformly mixed. Then, after adding the gypsum board material to this mixture and mixing uniformly, 150 mm × 180 mm ×
It was formed into a 9 mm board and dehydrated and dried at 80 ° C. until the weight became constant. The thus obtained test board was used as a test board, and the flexural strength, compressive strength and water resistance (water absorption) were measured.
Were obtained.

Further, for comparison, a test board was prepared by changing the blending ratio of the fine hollow glass spheres obtained from calcined gypsum and shirasu, or the blending amount of the water repellent or the aqueous emulsion, and similarly, the water absorption and the bending strength and Water resistance, water absorption, and appearance were measured.

The water absorption was measured by immersing the test board in water at 30 ° C. to absorb water, and calculating the water absorption from the water absorption after 24 hours according to the following equation.

In addition, measurement of bending strength and compression strength is based on JIS K-7203.
And JIS K-6911.

The performance of the gypsum board thus obtained is shown in Table-8. Sample Nos. 26 to 33 are Examples of the present invention, and Sample Nos.
34 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. Table 10 shows the results. In addition, the dispersion stability test was based on the following.

(Dispersion stability)

Aqueous emulsion 15 with solid content adjusted to 40% by weight
After putting 0 g in a 220 ml glass bottle and sealing, leave it in a constant temperature room at 25 ° C. for 6 months and leave it in a constant temperature room at 45 ° C. for 1 week, then measure the appearance, transmittance, viscosity and average particle size. The dispersion stability of the emulsion was evaluated. The appearance, transmittance, viscosity and average particle size were measured by the following methods.

Appearance: Visually evaluated at 25 ° C. according to the following criteria.

○: Transparent or translucent liquid △: Cloudy liquid ×: Cloudy paste or cloudy, separated into two layers Transmittance: Wavelength 800 using spectrophotometer (Digital Double Beam Spectrophotometer UVIDEC-320 manufactured by JASCO Corporation)
The absorbance under light irradiation of nm was determined, and the light transmittance (%) was calculated.

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

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

The aqueous emulsions of Samples 1-4, 8, 9, 12, 13, and 15-16 subjected to a strong heat dispersion stability test which was allowed to stand in a 45 ° C. Was formed, and the film properties and the performance as a compounding agent for hydraulic inorganic materials were measured according to Example 1. Transparency, water resistance, pressure-sensitive adhesive, solvent resistance (crosslinkability), mechanical strength, and evaluation as a compounding agent for hydraulic inorganic materials were all almost the same as the results of Examples 1, 2 and 3. was gotten.

FIG. 1 (A) and FIG. 1 (B) are graphs showing changes in the viscosity distribution before and after the static stability test.
Sample No. 5 in Table 1 was left at 45 ° C. for 1 week after standing test at 45 ° C., because it had many ultra-large particles and could not be measured due to poor dispersibility. The subsequent change in particle size distribution was shown and compared.

Further, Example 1 (Sample No. 1) and Example 1 (Sample No. 1)
After the aqueous emulsion of 5) was allowed to stand at 25 ° C. for 6 months, the change in low boiling components in the aqueous emulsion was analyzed using a gas chromatograph under the following conditions.

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

Gas chromatograph (GC-6AM type detector F made by Shimadzu Corporation)
ID) Column: Polapak Type Q 50cm (Waters Associates In
. c, Ltd.) Carrier gas: N ₂ 20 ml / min heating conditions: Initial 160 ℃ Final 230 ℃ heating rate 5 ° C. / min Hold Time 10 min FID Sensitivity: 10 ⁴ M.OMEGA.

[Brief description of the drawings]

FIGS. 1 (A) and 1 (B) show the products (samples) of the present invention, respectively.
No. 1) and the comparative product (Sample No. 5)
It is a graph showing the change of the viscosity distribution after standing at 6 degreeC and 6 months. 2 (A) and 2 (B) show the products of the present invention (sample N), respectively.
o.1) and the comparative product (Sample No.5)
It is a graph showing the change of the low boiling point component in the aqueous emulsion after standing at 5 degreeC and 6 months. The peaks in FIG. 2 (A) and FIG. 2 (B) are as follows. Is the peak of methanol in the solvent, is the peak of ethyl acrylate and methyl methacrylate of the raw material monomers, is the peak derived from the dimethacrylic acid ester of polyoxyethylene-P, P'-isopropylidene diphenyl ether (EO = 20) as the emulsifier, ,, And are peaks due to low boiling components not derived from the raw materials.

Claims (1)

(57) [Claims] (1) having an average particle diameter of 100 nm or less, having a crosslinked structure, having a glass transition temperature higher than a value calculated by a weight fraction method, and having a zeta potential of -30 mV or less; Characterized by comprising, as an essential component, an aqueous emulsion which is excellent over a long period of time.