JPH02141451A - Compounding agent for hydraulic inorganic material - Google Patents

Abstract

PURPOSE:To obtain a compounding agent for hydraulic inorganic material which is excellent in the improving effect of fluidity at a kneading time, water resistance, durability and appearance of a hardened body by constituting the title compounding agent of both aqueous emulsion having a cross-linking structure and specified average particle diameter and a polymer contg. sulfonic acid group as the essential components. CONSTITUTION:Aqueous emulsion having <=300nm average particle diameter and a cross-linking structure is produced by such a method that an unsaturated monomer (e.g., methyl methacrylate) and an unsaturated copolymerizable monomer (e.g., glycidyl methacrylate) are emulsion-polymerized. Then a compounding agent for hydraulic inorganic material is produced from both the obtained aqueous emulsion and a polymer having sulfonic acid group (e.g., polystyrene sulfonate, naphthalenesulfonate formalin condensate) as the essential components. This compounding agent is added to hydraulic inorganic material so that it is regulated to about 1-30 pts.wt. for 100 pts.wt. cement and utilized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a compounding agent for hydraulic inorganic materials which contains an aqueous emulsion and a polymer having sulfonic acid groups as essential components.

[Prior art]

In recent years, cement base 1, mortar, concrete
Hydraulic inorganic materials such as , cloud, and gypsum are used in large quantities in the fields of civil engineering, architecture, concrete secondary products, and the like. The purpose is to improve the adhesive strength, waterproofness, chemical resistance, mechanical strength such as bending strength and tensile strength, or abrasion resistance and durability of these hydraulic inorganic materials, and also to improve their structure. Many proposals have been made to add various compounding agents to improve the appearance of objects or molded products and increase their added value.

For example, JP-A-60-10306], JP-A-60-2
No. 51160, JP-A-60-173054, JP-A-5
7-6706+, JP-A No. 57-77059, JP-A-59-102480, JP-A-5849653, etc., disclose that styrene, vinyl chloride, and ethylene are used in hydraulic inorganic compositions such as mortar and cement. A combination of polymer dispersion using a terpolymer emulsion, an ethylene-vinyl acetate copolymer emulsion, a styrene-butadiene synthetic rubber latex, and a combination thereof;
The addition of various polymer compound formulations such as composite polymer emulsions has been disclosed.

Although these conventional methods have improved the physical properties and appearance of the hydraulic inorganic composition described above, they have not yet fully satisfied these various performances.

Therefore, as a method to solve these problems, the present inventors first applied a hydraulic inorganic material with an average particle diameter of 300 nm.
proposed a method of blending an aqueous emulsion with a crosslinked structure of less than m (Japanese Patent Application No. 62-4390;
-: No. 305367). However, subsequent research has shown that these methods have high lobby properties due to the fact that the aqueous emulsion used is ultrafine polymer latex particles, etc. Sometimes a large amount of lumps (agglomerates)
I found out that it can sometimes be generated. When the water/cemen 1 weight ratio is increased to improve fluidity in order to suppress lumps, new problems arise such as insufficient strength and poor durability of the cured product.

[Point 1] Point 1-1 of the present invention is different from the above-mentioned conventional compounding agent, in that it uses a hydraulic inorganic material, 1111. ! Fluidity when kneading the mixture and water 1. 1. It is possible to improve the appearance of cured inorganic materials (hereinafter referred to as cured bodies), and further improve various properties such as water resistance, solvent resistance, and durability. 1. To provide an inorganic material compound.

〔composition〕

The compounding agent for hydraulic inorganic materials of the present invention has (a) a water + 1 emulsion having a crosslinked structure with an average particle diameter of 300 nm or less, and (b) a polymer having a sulfonic acid group as essential components. It is characterized by

The aqueous emulsion, which is the first component of the formulation for hydraulic inorganic materials of the present invention, has an ilZ average particle diameter of 00n.
It is required that an essential component of the aqueous emulsion be less than 1 m, preferably 2000 m or more, and more preferably 1100 n or less.

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: + 00 nm or less, preferably 2
Since the diameter is limited to 00 nm or less, more preferably 100 nm or less, impregnation into hydraulic inorganic materials = 4. The properties or kneading properties are also good, and thermal adhesion, smoothness and gloss of the surface of the film and inorganic cured product, etc. It becomes possible to greatly improve the performance of the

If the average particle size exceeds 300 nm, 1ft of skin
The fusion properties (denseness) when +¥ (inorganic cured body) is formed are omitted, and the hydraulic inorganic cured body may contain a large amount of free water. Furthermore, the kneading properties with the hydraulic inorganic material are poor, and bleed defects of the aqueous emulsion occur, so the glossiness of the coating and the surface of the inorganic cured product, 'S1/
Since the lubricity may be lacking, the intended purpose of the present invention cannot be achieved.

Moreover, the second feature of the aqueous emulsion according to the present invention is:
The aqueous emulsion has a crosslinked structure within the particles and/or within the particles.

That is, in the aqueous emulsion of the present invention, within the particles and/or between the particles, for example, the functional groups of the raw material unsaturated monomers, or the functional groups of these and the emulsifier (i.e., ionic bonds, hydrogen bonds, condensation reaction or +l'4 reaction 1
．． It is presumed that it forms a film (cured product) with excellent transparency, adhesiveness, water resistance, and mechanical strength because it is crosslinked by ; ; Also, the formulation for hydraulic inorganic materials of the present invention The average molecular weight of the cross-linked aqueous emulsion, which is an essential component of the agent, is generally several hundred thousand or more, and in most cases it is several thousand, and some have a high degree of cross-linking. The amount ranges from several thousand blades to 1 billion, and even more than this (sometimes it shows a negative amount).

The present invention will be explained in more detail below.

The aqueous emulsion which is an essential component of the formulation for hydraulic inorganic materials of the present invention has an unsaturated content of 111. It can be easily obtained by emulsion polymerization of Qj.

Examples of the unsaturated monomer include (meth)acrylic esters represented by the general formula (1) (wherein R1 and 1 are hydrogen or methyl).

is an alkyl group having 1 to 18 carbon atoms), lower fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl acetate, acrylonitrile,
Nitriles such as methacryloni-1-lyl, styrene, α
- Styrene compounds such as methylstyrene and chlorostyrene, vinyl compounds such as vinyl chloride and vinyl bromide (, lj
, vinylidene filtrate, vinylidene bromide, etc., alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, etc.
, butadiene, taloloprene, isoprene, and other dienes, and vinylpyridine. Preferably, (meth)acrylic acid esters, lower fatty acid vinyl esters, nitriles, and styrenes are used.

In addition, in the present invention, as the unsaturated monomer to be copolymerized with the unsaturated monomer described in 1. Unsaturated monomers with reactive functional groups are preferably used to promote crosslinking during film formation, but even unsaturated monomers without reactive functional groups can be used in emulsion polymerization systems. It is also possible to use '41 unsaturated monomers by converting them into compounds having active hydrogen.

Unsaturated +1t Jil with such reactive functional group
Examples of the compound include compounds represented by the following general formulas (11) 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.

■ R, OH (where It, , l(7, R,, R,, R,, R7,
R,,R,,A,B,D,E,tl.

t2 and t3 are as follows.

L, l(2,; hydrogen j]'II child or methyl group R4;
Alkylene group having 2 to 4 carbon atoms R9; Direct bond, alkylene group having 1 to 3 carbon atoms.

Phenylene group or I6-substituted phenylene group! (6; oxygen
hydrogen, an alkylol group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms 1 (9; 1 to 5 carbon atoms) ~4 alkylene group A; methylene group or carbonyl group 1:l; -CH, O- or carboxyl group; hydrogen atom, alkyl group having 1 to 3 carbon atoms, carboxyl group, -C
ONHCHCH3 or 0OII -CONHCONH2 E; hydrogen atom, alkyl group having 1 to 3 carbon atoms, or -CH
7COO11 tl; real number t from 0 to 20; integer t from 0 or l; integer from O to ]0) General formula (II), (lit), (IV), (V), (V
Specific examples of the compounds represented by l), (Vll) and (■) include those shown below.

Examples of general formula (II) Glycidyl acrylate-I to glycidyl methacrylate Glycidyl acrylate-1-glycidyl allyl ether Examples of general formula (III) Hydroxyethyl acrylate Hydroxyethyl methacrylate Hydroxyethyl chloro 1-nate Hydroxypropylacrylate Hydroxypropyl methacrylate Le-1・10- (in the formula, ■, ., R11, R11, ■(,3,1(,4
, I(,5, I+, , , ao, R2, R3, R4, a, m and G are as follows.

R3゜; Alkylene group having 2 to 4 carbon atoms R1; Hydrocarbon group, phenyl group, amino group or carboxylic acid group which may have a substituent R□21R□6; Hydrogen or methyl group R13; Optional hydrocarbon group Ri4+Rt
s: Hydrogen or an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably R1,4 or R□
One of 5 is hydrogen and the other has 6 to 18 carbon atoms a1+a2, a, lR4; indicates the average number of added moles a
+182. R3: Real number from 0 to 50 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, preferably amine (salt), particularly preferably 1 ~realkanolamine salt m; ionic valence n of M; integer 85 from 1 to 10; real number ○ I -P-0- ■ OR, R OCnHzn-F, (LJg20 "IGI R1,7; hydrogen or Alkyl group with 1 to 2 carbon atoms R, 8; hydrogen or state (, oO← or g,; integer direction of 0 to 5; integer of 0 to 1.0 and y: real number of 1 to 5 Ls 1R20; hydrogen or alkyl group Y' having 1 to 20 carbon atoms; alkylene group having 3 to 8 carbon atoms, oxygen or carbonyl group It has a crosslinked structure,
Furthermore, in order to obtain a fine particle pre-crosslinked aqueous emulsion with excellent dispersion stability in which coalescence and aggregation of particles are suppressed over a long period of time at a zeta potential of 130 mV or less, emulsion polymerization of the above-mentioned unsaturated single substrate is necessary. As emulsifiers used in (a) the above general formulas (IX), (X), (XI), (Xll), (X
(b) a sulfonate-type emulsifier represented by the general formula (XV), and (c) a polyreactive emulsifier represented by the above-mentioned general formula (XVI). At least three components of the (meth)acroyl type emulsifier are essential components, (a)/(c)=971-17
9 weight ratio, preferably 471-174 weight ratio, (b)/
(a)+(C)=7/3-1/9 weight ratio, preferably 3
/2-1/4 double display ratio.

If the usage ratio of (a)/(c) is greater than 971,
The crosslinkability and (or dispersion stability) 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 of the film formed, 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, the particles coalesce and aggregate to become cloudy, and even transparent or translucent microparticles become cloudy. Even if an emulsion is formed, the zeta potential is negative and small.
When stored for a long period of time, particles easily coalesce and agglomerate, producing coarse particles that become extremely cloudy, and furthermore, the aqueous emulsion may undergo layer separation or its viscosity may increase significantly. .

When these emulsifiers are used in the proportions listed in 1, they become ultrafine particles, have a crosslinked structure, have a highly negative zeta potential, and further suppress coalescence and aggregation between particles for a long period of time. It is possible to produce an aqueous emulsion which has excellent dispersion stability and also has a glass transition temperature higher than the value calculated by the weight fraction method.

In addition, the appropriate amount of these emulsifiers to be used is about 0.1 to 15% by weight of the unsaturated monomer to be emulsion polymerized.
Preferably it is 0.5 to 10% by weight.

In addition, known anionic, nonionic and cationic surfactants may be added as necessary, and specific examples thereof include higher alcohol alkylene oxide adducts, alkylphenol oxide alkylene 20 adducts, and styrenated phenol. Alkylene oxide adducts and their sulfate types, olefin sulfo 1-types such as α-olefins, quaternary ammonium salt types of long chain alkyl amine alkylene oxide adducts and di-long chain alkyl amine alkylene oxide adducts, N −(1,
, 2-dicarboxyethyl) N-octadecylsulfonic acid monoamide sodium salt, dialkyl sulfosuccinate, bleached ceramic resin, 4-hydroxy-4,5
Examples include organic and inorganic salts of dicarboxypentadecanoic acid or 4,5-dicarboxy-pentadecanolide.

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

In order to obtain the aqueous emulsion which is the first essential component of the formulation for hydraulic inorganic materials of the present invention, a conventionally known emulsified compound Y You can use the system as is. For example, in the presence of a polymerization initiator equivalent to 0.1 to 5 weight of unsaturated monomer t-form, a polymer of an unsaturated monomer is emulsified and dispersed in water at a concentration of 10 to 60 weight 1%, and emulsion polymerization is carried out. All you have to do is make it happen.

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'-ambis(N
, ~dimethylene-isobutyramidine) and its salts, 4°4'-azobis(4-cyanovaleric acid) and its salts, and other water-soluble azo initiators can be used.

In particular, when a water-soluble azo-based initiator described in item 1 is used, it is easy to prepare an aqueous emulsion, which is the first essential component of the hydraulic inorganic material formulation of the present invention.

The second component of the hydraulic inorganic material formulation of the present invention is a sulfonic acid group-containing polymer.

Examples of such polymers include lignin sulfonate, naphthalene sulfonate formalin condensate, sulfonated melamine resin, polystyrene sulfonate, and the like. Among these, polystyrene sulfonate is particularly excellent. Counter ions for these salts include alkali metals, alkaline earth metals, amines, alkanolamines, and the like. Particularly preferred are amines and alkanolamines, specifically, alkyl monoamines having 1 to 5 carbon atoms, alkyl diamines having 1 to 5 carbon atoms,
Examples include alkyl triamines, monoalkanolamines having 2 to 12 carbon atoms, dialkanolamines having 2 to 5 carbon atoms, and 1-dialkanolamines. From the viewpoint of preventing acidification of the hydraulic inorganic material, it is preferable to use the alkaline substance that generates these counterions in an amount of at least 1:3 to 3:3 with respect to the sulfonic acid group.

As the polystyrene sulfonate preferably used in the present invention, a styrene sulfonate monomer is homopolymerized by a known method or copolymerized with an ethylenically unsaturated carboxylic acid or an anhydride thereof. Examples include homopolymers or copolymers of polystyrene sulfonate obtained by polymerization. Furthermore, carbon chain lengths of 2 to 12 obtained by reacting polystyrene or polystyrene with olefins or alcohols having 2 to 12 carbon atoms in the presence of a catalyst such as activated clay or sulfuric acid.
Partially alkylated polystyrene partially alkylated with an alkyl group of 0.01 to 0.3 mole per benzene, or styrene obtained by copolymerization with an ethylenically unsaturated carboxylic acid copolymerizable with styrene or an anhydride thereof. The copolymer, which is a copolymer of Separately,
Neutralize and 1! ) Polystyrene sulfonate may be used.

The molecular weight of the polystyrene sulfonate is not particularly defined, but is 5,000 to 100.
A range of 000 is preferred.

Further, the sulfonation rate of polystyrene sulfonate obtained by sulfonating polystyrene or the like is desirably 70% or more from the viewpoint of improving fluidity.

If it is less than 70%, the fluidity will be poor and the amount of air mixed in will also increase. Further, it is desirable that the content of low polymer molecules of 4 or less bodies in the polystyrene sulfonate is 30 weight 2 or less. If it exceeds 30% by weight, it is not preferable because the fluidity becomes low and the properties of the hydraulic body are impaired.

The ratio of the aqueous emulsion (a) to the sulfonic acid group-containing polymer (b) is (a)/(b) in terms of solid content weight ratio!
19, 9! l/+1, 0]~90/10,
Preferably +19. From fllo, 1-9773! 5
The ratio is preferably 99.710.3-9515.

When (a)/(b) is larger than 99.9910.01, many lumps will be formed and hardened when mixing hydraulic inorganic materials, water-based emulsions, water, fine aggregates, coarse aggregates, etc. This is not preferable because it reduces the strength of the body, lacks fluidity, and has poor durability. Also, (a)/(b) is 90/10
When it is smaller, there are problems such as the original appearance of the cured product being damaged and the (warm) water resistance of the cured product being reduced.

The compounding agent for hydraulic inorganic materials of the present invention may include the components listed in 1 above at the time of blending with the hydraulic inorganic material,
The aqueous emulsion (which is the first essential component of the present invention)
Before or after the preparation of a), a mixture of the second component, the polymer (b) containing a sulfonic acid group, may be mixed and kneaded with the hydraulic inorganic material.

Furthermore, for the purpose of preventing the occurrence and promotion of rust on metals such as iron in hydraulic inorganic materials and further increasing durability, 1-hydroxy-alkane-1,1- represented by the following general formula is used. Diphosphonic acid or a salt thereof may be mixed and kneaded.

=25 Examples of the salt in this case include alkali metals, alkaline earth metals, amines, and alkanolamines. The blending amount of this I-hydroxy-alkane-1,1-diphosphonic acid or its salt is 0.01 with respect to the hydraulic inorganic material.
-10wt%, preferably 0.1-2wt%.

The hydraulic inorganic material compounding agent of the present invention is added to the hydraulic inorganic material in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 5 to 15 parts by weight, based on 100 parts of cement. It is appropriate to add and use.

If the blending amount is less than 1 part by weight, the abrasion resistance, strength, and durability of the hydraulic body cannot be improved. On the other hand, if it is too large, a large amount of lumps may be formed, and the hydraulic inorganic compound (cemen 1- (paste, mortar, concrete, etc.) is undesirable because the cured product lacks wear resistance and becomes sticky.

In addition, the compounding agent for hydraulic inorganic materials of the present invention may include nonionic, anionic or cationic polymer substances, coloring pigments, clearing agents, preservatives, pH adjusters, plasticizers, Early hardening agents, slow hardening agents, conductive (antistatic) agents and reinforcing agents may be used as auxiliary additive ingredients.

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

Examples of anionic polymeric substances include anionized hydroxyethyl cellulose, anionized starch, anionized guar gum, anionized x1-sane, carboxymethyl cellulose, anionized polyvinyl alcohol, polycarboxylic acid salts, oxycarboxylic acid salts, and the like.

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 in combination of one or two or more types, but the amount to be added is determined based on the emulsion polymerization target. It is appropriate to use it in an amount of 0.05 to 5 weight percent, preferably 0.1 to 3 weight percent, based on the monomer.

Examples of color pigments include titanium white, titanium yellow,
Red red, iron black, ultramarine, chrome green,
Examples include purple red pepper. As a chelating agent, ethylene diamine salt, 1-hydroxyethane diphosphate, as a plasticizer, phthalate ester, phosphate ester, as an early hardening agent, calcium chloride, as a slow hardening agent, gluconate, as a reinforcing agent. , carbon fiber, polystyrene fiber, etc. can be used.

〔effect〕

The compounding agent for hydraulic inorganic materials of the present invention has (a) an aqueous emuldimine with an average particle size of 300 nm or less and a crosslinked structure and (b) a sulfone-ugly group-containing polymer as essential components, and therefore has good hydraulic properties. It is possible to improve the fluidity when kneading the inorganic material mixture, eliminate the occurrence of lumps, and further improve the aesthetic appearance of the cured body (layer) of the hydraulic inorganic material. In addition, it can further improve mechanical strength properties such as water resistance, solvent resistance, and abrasion resistance, and has extremely high durability, so it has extremely high practical value. .

Therefore, the formulation for hydraulic inorganic materials of the present invention can be used as base materials for inner and outer walls of architectural structures, adhesives for tiling, joint materials for tiling, flooring materials, anticorrosion lining materials such as anticorrosive ALC reinforcing bars, and water storage materials. Waterproofing materials for tanks, pools, silos, tennis court bases, etc., deck covering materials for ship decks, pedestrian bridge floors, bridge dyed decks, etc., acid-resistant hume pipes, special concrete moldings made by GltC, bus terminals, 1
- Semi-rigid roads in tunnels, factories, etc., spraying of concrete base with carbon fiber and polyvinyl alcohol fiber, protective coating material, conductive coating material with carbon fiber and metal powder, electromagnetic shielding material,
Ultra-high-strength molded products, heavy-duty anti-corrosion coating materials for ship haus tanks, etc.
Mortar floating repair materials, cable-stayed bridge wire materials, decorative skin, roof tiles,
It exhibits extremely efficient performance when used in the production of chemically molded products such as interlocking.

〔Example〕

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

Example 1 [Preparation of aqueous emulsion] Emulsifier 8 shown in Table 1 was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen introduction tube, and a dropping funnel.
．． 0 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-methylol acrylamide and 1.5 parts by weight of water was prepared. 15 parts by weight of the mixture was added to the reaction vessel and emulsified at 40"C for 110 minutes. After raising the temperature to 60°C, the polymerization initiator was added with potassium persulfate 3.OX 10-3 shown in Table 1.
mo1. e/aqueous phase Q, sodium thiosulfate3. OX1
0-'mole/aqueous phase Q and aqueous phase copper acid 5.0×10-'
A KPS-based initiator (KPS system) or 2,2'-azobis (N.

N'-dimethyleneisobutyramidine hydrochloride (VA-0
44) to 9. OX was dissolved in 48.5 bases of water to give 10-3 moles of OX/aqueous phase Q, added to the reaction vessel, and the remaining unsaturated monomer was immediately poured into the reaction vessel continuously for 30 minutes. It was added dropwise and polymerization was carried out at 60°C.

After dropping the unsaturated monomer, it was aged at 60°C for 90 minutes,
After cooling to room temperature, the mixture was adjusted to pl+=9 with 1-liethanolamine to prepare an aqueous emulsion.

[Adjustment of polystyrene sulfonate]

Into a reaction vessel equipped with equipment similar to the glass reaction vessel used in the preparation of the aqueous emulsion, 58% dichloroethane was added.
5 parts by weight and 245 parts by weight of polystere (weight average molecular weight:
5,500) and stirred and dissolved at room temperature. Next, while maintaining the reaction temperature at 30° C., 35 weight of sulfuric anhydride was added dropwise, and after the addition was completed, aging was carried out at the same temperature for 30 minutes.

After aging the cotton Y, the poly:31 styrene sulfonic acid produced was filtered, the product was thoroughly dried under reduced pressure, and dichloroethane was distilled off. Then, it was prepared with 20 parts by weight of thorium hydroxide aqueous solution so that pl+ was 8, and the solid content concentration of calcium polystyrene sulfonate was 130 parts by weight (1).
% aqueous solution.

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

[Evaluation of water-based emulsion]

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

Average particle size: Coulter Submicron Particle Analyzer (Coulter Electronics, Inc., USA, Coul
, 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 2anX14 (1) glass plate and air-dried at 25°C. 111k of skin obtained in this way are 2anX4an
The sample was cut into pieces, immersed in a Petri dish filled with benzene at 20°C for 48 hours, and evaluated as follows based on the degree of swelling and solubility of the film.

O: The area of the film is equal to or slightly swollen than the film area (2(1)×4) before immersion in benzene.

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

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

[Preparation and performance evaluation of hydraulic inorganic materials] Polymer cement mortar was prepared using silica sand, cement, water, and the aqueous emulsion described in "-" and polystyrene sulfonate in the proportions shown below, and the fluidity and clumps of this polymer cement mortar were evaluated. 3tk, thick coating property, polymer bleed, appearance (aesthetic appearance) of the cured product, seawater resistance, solvent resistance, acid resistance, and abrasion resistance were evaluated according to the following criteria.

No. 7 silica sand 1150 parts by weight i1 (parts;) 4 No. 8 silica sand* 25 parts by weight Cement 1-9275 parts by weight Aqueous emulsion ], ], , 25
Part by weight Polystyrene sulfonate 0.105 parts by weight Water 42.85 Part by weight Defoaming*J Landcemen 1-) Fluidity: 56mm, 6], mm, 66nwn, 7],
mm, 76 mm, and a glass plate with concentric circles of radius every 5 nwn'' Second, the diameter: (Onwn and 50 mm
, Height 35Iff11 and Wall Thickness: (Place the hollow cone made of Vine as shown in the picture, sufficiently deform the polymer cement mortar so that no air is sucked into it, and immediately pull out the hollow cone. Measure the length that the polymer cement mortar is cast onto the glass board and the height of the polymer cement mortar.

Next, for the polymer cement mortar that has sufficiently maintained its truncated conical shape, a mayonnaise container filled with 1 kg of silica sand is gently placed on top of the polymer cement, a load is applied, and the polymer cement 1 to mortar is The length of casting on the glass plate and the height of the polymer cement 1-mortar were determined as tl.

Clumping amount: Measures the thickness of polymer cement mortar without sag when spraying or pipe-lining polymer cement mortar as the outer wall of a double-reinforced concrete building structure. did.

Polymer bleed error +-: Take 500 ml of polymer cement mortar just after making it into an IQ beaker, let it stand for 10 minutes, and then visually check the presence or absence of polymer bleed in the upper layer of polymer cement 1 to mortar. I judged it.

Aesthetics: External walls sprayed or plastered with polymer cement mortar after Material Ordinance 2811; 35:36 - Judging visually.

Polymer cement mortar immediately after preparation with water resistance, seawater resistance, and solvent resistance 250. ■ Fill a 150-disposal cup (pp) manufactured by Iuchi Seieido Co., Ltd. uniformly to prevent air from being mixed in.

Next, after standing for 2 days, the formwork was cut out, and after being left standing at room temperature for another 26 days (wood age), the cured product was placed in a 500mQ beaker filled with 25°C tap water, seawater, and benzene for 1 year. The surface of the cured product was observed and evaluated based on the following criteria.

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

△: Mortar surface lacks luster.

×: Mortar surface is whitened.

Acid resistance: d1 of water resistance and seawater resistance after 28 days of age
A specimen equivalent to that used for the q constant was immersed in a 1 wt Da aqueous sulfuric acid solution for 28 days, and evaluated based on 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.

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

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

Wear resistance: using the above mortar composition, 50ITITl
The cured product was prepared to have a cylindrical shape with a diameter of 50 mm, and after 28 days, the cured product was placed on a 10-mesh sieve and shaken for 2 hours using the rotary tube large shaking method (manufactured by Kabiko Seisakusho).
After shaking for a minute, the abrasion resistance was evaluated using the following formula.

Abrasion resistance (wt%) - xl, 00 A: Weight before shaking (g) B: Weight after shaking (g) Durability: Core equivalent to that used for abrasion resistance evaluation was 10Q Put it in an autoclave of 1olIwI+11
After reducing the pressure to below g and confirming that there are no leaks, carbon dioxide gas was introduced into the autoclave to a concentration of 5%, air was brought to normal pressure, and the inside of the autoclave was heated to 30°C and 60% R. , l+, and the temperature and humidity were adjusted so that the temperature and humidity were adjusted to be . After standing still, the core was cut into a semi-cylindrical shape, a 1z phenolphthalein-alcohol solution was sprayed onto the cut surface, the depth at which the cut surface turned red was measured, and evaluation was made according to the following criteria.

O: The entire cut surface of the cured product is red, or the surface is 0.
．． From the 2 to 0.5 mark, the area is divided into deeper parts and turns red.

Δ: Reddishing occurs from 0.6 to 1.0(7) on the surface of the cured product to the deep part.

x: The surface of the cured product is reddish from 2.0 cm onwards to the deep part, or the cut surface is not reddished.

Table 1 shows the properties of the aqueous emulsion thus obtained and the performance of the polymer cement mortar.

Samples Nil ] to 4 are examples of the present invention, and are found to be good as compounding agents for hydraulic inorganic materials.

Note that samples Nα5 to Nα7 and 7′ are comparative examples.

In addition, as a substitute for the polystyrene sulfonate used in the examples of samples Nα1 to 4, naphthalene sulfonate formalin condensate (Kao Mighty 150), sulfonated melamine resin (Hozolith Bussan Exhibition: NL-4000), and lignin sulfonic acid were used. Salt (manufactured by Sanyo Kokusai Pulp; Sunflow PS
) also obtained almost the same results as samples Nα1 to Nα4.

Example 2 Monotriethanolamine salt of stearyl 2-hydroxy-3-allyloxy-1-propylsulfosuccinate 4 parts, branched C10-14 alkylbenzenesulfonic acid triethanolamine salt 1.96 weight parts, xylene sulfonic acid triethanolamine salt 0.04
Part by weight, polyoxypropylene polyoxyethylene P,
2.0 parts by weight of P'-isopropylidene diphenyl ether dimethacrylic ester (POP=2, EOP=18) as an emulsifier, 135 parts by weight of ethyl acrylate, 15 parts by weight of methyl methacrylate, 4.0 parts by weight of N-methylol acrylic acid amide. An aqueous emulsion was prepared by emulsion polymerization of an unsaturated monomer consisting of 5 parts by weight and 1.5 parts by weight in the same manner as in Example-1.

On the other hand, polystyrene with a weight average molecular i of 7,000 was
% alkylated partially hexylated polystyrene was sulfonated according to Example 1, and neutralized with triethanolamine to obtain partially hexylated polystyrene sulfonic acid triethanolamine salt. (Sulfonation rate: 86z) Next, these (a) aqueous emulsions were blended with (b) partially hexylated polystyrene sulfonate in the solid content weight ratio as shown in Table 2, and this was prepared in the same proportions as in Example 1. Polymer cement 1 to mortar was prepared. Then, in the same manner as in Example 1, the performance of Polymer Cement 1 as a mortar was evaluated. The results are shown in Table-2. Samples Nα9 to II are examples of the present invention, and the blending ratio of the aqueous emulsion and polystyrene sulfonate is 99.9910.01 to 90.
It turns out that /10 is appropriate.

Note that samples NQ8 and 12 are comparative examples.

Example 23 The following emulsifiers 1 and 2 shown in Table 3 and the unsaturated monomer mixtures 1 and 2 shown below were prepared, and the conditions shown in Table 3 were prepared according to Example 1. Perform emulsion polymerization with
An aqueous emulsion was obtained and the emulsion was adjusted to a pl+ of 9 with triethanolamine.

On the other hand, a copolymer with a weight average molecular weight of 20,000 and a molar ratio of styrene and maleic anhydride of 2.0 was prepared in Example 1.
Sulfonation etc. were carried out in the same manner as above to obtain polystyrene sulfonic acid-maleic anhydride triethanolamine salt. The sulfonation rate of this styrene was 92.5%.

Next, polymer cement 1- Prepare mortar,
We evaluated its performance. The results are shown in Table 3. Sample NQ1
Examples 3 to 16 are examples of the present invention, and it can be seen that the polymer cement mortar to which the compounding agent for hydraulic inorganic materials of the present invention is added has excellent thixoisomerization and lobby properties. Sample Nα17~
18 is a comparative example.

471 Example 4 Using the compounding agent for hydraulic inorganic materials consisting of the aqueous emulsion of Example 2 and the solid content weight ratio of polystyrene sulfonate of 97.72/2.28, the Architectural Institute of Japan JAS
The fluidity of concrete was evaluated in accordance with S5T-402, and the hardened body of Hokono Concrete 1- was molded in accordance with jTs A/08. After 28 days, the durability (medium) was evaluated in accordance with Example 1. The sexualization test) was evaluated.

The above concrete has excellent fluidity, compressive strength, mechanical strength such as 1111 strength, and red coloration in the carbonation test, which can be seen on the entire cut surface of the hardened concrete, compared to base concrete without additives, and has excellent durability. Ta.

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

Example 6 In the preparation of the hydraulic inorganic material of Example 1, polystyrene sulfonic acid triethanolamine salt (however, the amount of triethanolamine was 1.2 times the equivalent of the sulfonic acid group) was used instead of polystyrene sulfonic acid Ca salt. 0.15 parts by weight, and l-hydroxyalkane-1-1- shown in Table 4
Diphosphonic acid or 1-hydroxyalkane-1-1-
Diphosphonic acid triethanolamine salt (however, the amount of triethanolamine is 4.2 times the equivalent of the phosphonic acid group) &0
．． A polymer cement mortar was prepared in exactly the same manner as in Example 1 except that 3 parts by weight was added.

Regarding the polymer cement mortars obtained in Examples 5 and 6 above, the antirust effect was measured according to Appendix 2 of JIS A6205 [Method for testing accelerated corrosion of reinforcing bars in concrete]. These results are shown in Table-4. In addition, in the preparation of the hydraulic inorganic material in Example 1, a sample prepared in exactly the same manner as in Example 1 except that polystyrene sulfonate was not added was used as a comparative example (sample No. 26). If the rust was significantly less, it was marked as 0 if the O1 was less, and if it was the same, it was marked as ×.

Table-4

Claims (2)

[Claims] (1) A compounding agent for hydraulic inorganic materials having an average particle diameter of 300 nm or less and comprising an aqueous emulsion having a crosslinked structure and a polymer having a sulfonic acid group as essential components. (2) The compounding agent for hydraulic inorganic materials according to claim 1, wherein the polymer having a sulfonic acid group is a polystyrene sulfonate.