JPS638253A - Cement composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention relates to a cement composition that produces a hardened cement product with excellent adhesive properties, elasticity, waterproof properties, etc. using an aqueous emulsion of an acrylic acid resin. It is.

[Conventional technology]

Traditionally, synthetic resin aqueous emulsions have been added to cement compositions used for coating and finishing buildings, etc., to prevent shrinkage cracks in the resulting cured cement, provide waterproofing properties, and improve adhesion. .

Effects such as improved impact resistance, improved abrasion resistance, and provision of elasticity have been obtained. Examples of the synthetic resin aqueous emulsion include synthetic rubber latex, acrylic emulsion,
Ethylene/vinyl acetate emulsion, ethylene/vinyl chloride emulsion, etc. are used.

Among these emulsions, synthetic rubber latex has excellent water resistance, cement alkalinity resistance, but poor ozone resistance, heat resistance, and weather resistance, so it is not used very often. It cannot be said to be an effective cement admixture. In addition, although ethylene/vinyl acetate copolymer resin has excellent adhesive properties, ethylene/vinyl acetate emulsions have poor water resistance, cement alkaline resistance,
It has a characteristic of poor weather resistance, and cannot be said to be an effective cement admixture. Ethylene/PVC emulsions also have excellent adhesive properties and cement alkali resistance, but have poor heat resistance and weather resistance, and cannot be said to be effective cement admixtures. On the other hand, acrylic emulsions have excellent resin properties in almost all respects, and are widely used as the overall best cement admixtures.

[Problem that the invention seeks to solve]

As mentioned above, acrylic emulsions are widely used as excellent anti-inflammatory agents, but attempts have been made to further improve their performance. For example, for the purpose of increasing the adhesive strength of the acrylic resin used in the above emulsion and further improving the adhesiveness of the cement hardened product, ethylenically unsaturated jllff having carboxyl groups and glycidyl groups is used.
Proposed methods include copolymerizing i-form or cationic ethylenically unsaturated monomers (e.g., alkylaminoethyl methacrylate) or adding cationic surfactants or cationic protective colloids to the emulsion to impart cationic properties. has been done. However, the improvement in adhesion of a hardened cement body by such a method is still insufficient depending on the field of application. Namely, glazed porcelain tile surfaces, plastic flooring materials (epoxy resin flooring, urethane resin flooring, vinyl chloride resin flooring, etc.)
It has poor adhesion to asphalt concrete surfaces, steel plate 2 plywood, old cement concrete and cement mortar surfaces, etc., so it is difficult to use it for coating and finishing surfaces of these materials.

Furthermore, for the purpose of increasing the elasticity of the cured cement product, a method has been proposed in which a soft acrylic resin with a low glass transition temperature is selected as the acrylic resin used in the acrylic emulsion, and the amount used is increased. According to this method,
Although a considerable effect can be expected, in reality, if the acrylic resin used is a soft one with a low glass transition temperature, the adhesion of the hardened cement will decrease, so Naturally, there are limits to the use of these materials, and the desired effect cannot be obtained, and only a certain degree of improvement in elasticity can be obtained. In particular, as mentioned above, as a result of restrictions on the use of materials with a low glass transition temperature, improvement in elasticity at low temperatures is insufficient, and the actual situation is that practical engineering is subject to various restrictions.

An object of the present invention is to provide a cement composition that can be used as a cured cement product that exhibits excellent adhesion to various adherends and exhibits excellent elasticity in a wide temperature range including low temperature ranges. .

[Means for Solving the Problems] In order to achieve the above object, the cement composition of the present invention has a structure in which the following components A and B are the main components.

(A) having at least one of a repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3) as main components, An aqueous emulsion of acrylic acid resin with a glass transition temperature of 10°C or less.

(B) Cement.

That is, the cement composition of the present invention contains an aqueous emulsion of an acrylic resin having the above repeating unit as a main component and having a glass transition temperature of 10° C. or less,
The acrylic acid resin is in the form of particles and has cationic properties, so when a cement composition is applied to the surface of an adherend, it efficiently adsorbs to the anionic cement particles. As a result, the distribution or arrangement of cement particles and acrylic acid resin particles becomes uniform. In this state, a crosslinking reaction occurs due to the alkali of the functional group HX present on the surface of the acrylic acid resin particles, and it forms a strong bond between resin molecules, resin particles, cement, and even the adherend. The hardened cement exhibits excellent adhesion and adheres strongly to adherends. This remarkable improvement in adhesion is due to the use of acrylic acid resins with low glass transition temperatures (
This makes it possible to use resins with a low glass transition temperature such as those mentioned above without any problems, thereby making it possible to improve elasticity in low-temperature ranges.

As described above, the greatest feature of the present invention is the use of an aqueous emulsion of an acrylic resin containing the above-mentioned repeating unit as a main component.

An aqueous emulsion of an acrylic acid resin containing the above-mentioned repeating unit as a main component can be prepared by using, for example, an acrylic acid alkyl ester and a methacrylic acid alkyl ester having an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms alone or in combination. However, these monomers and the following general formula (4)
Alternatively, it can be produced by copolymerizing the alkali crosslinkable quaternary ammonium salt monomer represented by (5) alone or in combination according to a known method for producing an aqueous acrylic acid resin emulsion. .

The above-mentioned acrylic acid alkyl ester having an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms.

Typical examples of methacrylic acid alkyl esters are as follows. acrylic acid methyl ester,
Acrylic acid ethyl ester, acrylic acid propyl ester, acrylic acid phthyl ester, acrylic acid amyl ester, acrylic acid hexyl ester, acrylic acid 2-ethylhexyl ester, acrylic acid n-octyl ester, acrylic acid decyl ester, acrylic acid lauryl ester, acrylic Acid cyclohexyl ester, methyl methacrylate, ethyl methacrylate 2 propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, methacrylic acid Decyl ester, methacrylic acid lauryl ester. These may be used alone or in appropriate combinations.

In addition, if necessary, other unsaturated monomers copolymerizable with these, such as styrene and its derivatives, acrylonitrile, methachronitrile, acrylic acid, methacrylic acid, vinylpyridine, vinylpyrrolidone, and hydroxyalkyl acrylate.

In combination with acrylamide and its derivatives, methacrylamide and its i3 form, alkylaminoacrylate, alkylaminomethacrylate, N,N-dialkylacrylamide, N,N-dialkylmethacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, etc. Good too.

As representative examples of the alkali-crosslinkable quaternary ammonium salt monomer of the above general formula (4) to be copolymerized with the above (meth)acrylic acid alkyl ester, various epihalohydrin adducts and inorganic or organic anions shown below are used. salts, e.g. chloride.

Bromide, sulfate, nitrate, acetate, propionate, benzene sulfonate.

Examples include lauryl sulfonate.

(Epihalohydrin adduct) Dimethylaminoethyl methacrylate/epihalohydrin adduct [In general formula (4), R=C113, A=
-0-, n=2, R+, Rz=CH3, X=Cl
.

Compounds that are Br or I, the same notation will be used hereinafter]
, diethylaminoethyl methacrylate/epihalohydrin adduct, dimethylaminopropyl methacrylate/
Epihalohydrin adduct, dimethylaminoethyl acrylate/epihalohydrin adduct, diethylaminopropyl methacrylate/epihalohydrin adduct, dimethylaminoethyl acrylate/epihalohydrin adduct,
Diethylaminopropyl acrylate/epihalohydrin adduct, dimethylaminopropyl methacrylamide/
epihalohydrin adduct, diethylaminopropyl methacrylamide/epihalohydrin adduct, dimethylaminoethyl methacrylamide/epihalohydrin adduct,
Diethylamine propylacrylamide/epihalohydrin adduct.

Dimethylaminopropylacrylamide/epihalohydrin adduct.

Among the alkali crosslinkable quaternary ammonium salt monomers represented by the above general formula (4), dimethylaminoethyl methacrylate/epichlorohydrin adduct, dimethylaminoethyl acrylate/epichlorohydrin adduct,
The chlorides or nitrates of dimethylaminopropyl methacrylate/epichlorohydrin adducts, diethylaminepropylacrylamide/epichlorohydrin adducts, and dimethylaminopropylacrylamide/epichlorohydrin adducts are easy to produce or obtain, and are acrylic oxygen resins (common It is particularly suitable for use because it gives a polymer).

These compounds of general formula (4) easily undergo a dehydrohalogenation reaction by adjusting the pH, etc., and are converted into compounds of general formula (5) having an epoxy group at the terminal. The compound of formula (4) can also be used as an alkali-crosslinkable hyalomer in the production of the copolymer of the present invention, and is used alone or in combination with the compound of general formula (4). As described above, the compound of the above general formula (5) is usually one derived from the compound of the above general formula (4). However, rather than using the compound of general formula (5) alone or in combination with the compound of general formula (4),
It is more convenient for production to use the shrimp halohydrin form alone.

The amount of the alkali-crosslinkable quaternary ammonium salt monomer of the above general formulas (4) and (5) used (copolymer amount) is based on the weight of the alkali-crosslinkable quaternary ammonium salt monomer of the above general formulas (4) and (5). It is preferable to set the proportion of the class ammonium salt monomer to 0.5 to 10%. Thereby, in the acrylic acid resin, the general formula (1).

The repeating unit represented by (2) accounts for 0.5 to 10% of the entire acrylic resin based on weight. A more preferable range is 1 to 7% (by weight, the same applies hereinafter).

That is, if the above value is less than 0.5%, the effect of improving adhesiveness and elasticity to the hardened cement product is not sufficient;
%, the degree of crosslinking becomes too high, and the copolymer and eventually the hardened cement tend to become brittle.

The above alkali crosslinkable quaternary ammonium salt monomer, (
The copolymerization reaction with meth)acrylic acid alkyl ester is
As already mentioned, the process is carried out in accordance with the production of a known aqueous acrylic ester copolymer emulsion, but to explain in more detail, the process is carried out in a reaction vessel equipped with a 'fA stirrer whose internal temperature can be adjusted using a jacket, etc. The above monomers are added and a polymerization reaction is carried out under normal pressure. The reaction is carried out at the radical generation temperature of the polymerization initiator, generally from 50 to 80''C, for 3 to 8 hours.

During this polymerization reaction, a polymerization initiator, a surfactant, a protective colloid, a chain transfer agent, a buffer, and the like are added to the reaction system in the form of an aqueous solution or dispersion.

As the polymerization initiator, a peroxide or a combination of a peroxide and a reducing substance is generally used. Examples of peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide, and examples of reducing substances include acidic sodium sulfite, sodium thiosulfate, and ferrous hydrosulfide. The amount of polymerization initiator used is 0.02% of the total monomers used.
The ratio is set to ~5%.

Furthermore, as the surfactant, all commonly used surfactants (nonionic, anionic, and cationic) can be used, but in this invention, especially nonionic or cationic surfactants can be used. It is preferable to use it, and the properties of the acrylic acid resin obtained can thereby be exhibited most effectively. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, oxyethylene oxypropylene block polymer, etc., and cationic surfactants include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, Examples include distearyldimethylammonium chloride and alkylbenzyldimethylammonium chloride. Anionic surfactants can also be used, although they are not as effective as the nonionic or cationic surfactants mentioned above. As such,
Sulfate ester alkali salts of higher alcohols, alkylbenzenesulfonic acid alkali salts.

Alkylnaphthalene sulfonic acid alkali salt, polyoxyethylene alkyl sulfate alkali salt.

Examples include polyoxyethylene alkylphenyl sulfate alkali salts.

In addition, almost all known water-soluble polymers can be used as the protective colloid, and typical examples include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, sulfonated partially saponified polyvinyl alcohol alkali salt, and sulfonated completely saponified polyvinyl alcohol. Examples include saponified polyvinyl alcohol alkali salts, water-soluble cellulose derivatives such as methyl cellulose and hydroxyethyl cellulose, as well as polypropylene glycol and polyethylene glycol. The amount of protective colloid used is 0 based on the total monomer used.
．． The content is preferably 2 to 10%, more preferably 2 to 5%.

As a buffering agent, monobasic sodium phosphate, potassium bicarbonate, sodium pyrophosphate, potassium pyrophosphate, tribasic sodium phosphate,
Examples include sodium acetate, and the amount used is set at 0 to 5% based on the total fecal amniotic mass.

In this way, an aqueous emulsion of acrylic acid resin is produced. The acrylic acid resin is dispersed in the form of particles in the aqueous emulsion, and it is preferable to set the particle size to a range of 0.01 to 1 μm. Moreover, it is preferable to set the aqueous emulsion so that the acrylic acid resin (solid content) accounts for 20 to 70%. The glass transition temperature of the acrylic acid resin is set to 10°C or less, preferably 0°C or less, and more preferably -10°C or less. That is, the glass transition temperature of an acrylic acid resin is mainly determined by the size of the alkyl group in the (meth)acrylic ester monomer, and becomes lower as the number of carbon atoms in the alkyl group increases. Therefore, in this invention, the alkyl group of the (meth)acrylic ester has 1 to 1 carbon atoms as described above.
12, and care is taken to ensure that the glass transition temperature of the produced acrylic acid resin is 10°C or less. When the glass transition temperature exceeds 10° C., the main skeleton of the resulting resin becomes too hard, and the cured resin becomes brittle and lacks elasticity, so that the elasticity of the cured cement product does not improve. Therefore, the acrylic acid resin needs to have a glass transition temperature of 10° C. or lower.

In addition, acrylic acid resins with relatively high glass transition temperatures,
For example, for resins with a glass transition temperature exceeding 10°C, a plasticizer may be added to lower the glass transition temperature to 10°C or less, or plasticizers may be added to lower the glass transition temperature to below 10°C, or plasticizers may be added to A blend of the agent and the (meth)acrylic ester may also be used. As the plasticizer used, commonly used plasticizers such as dibutyl phthalate, dioctyl phthalate, trimethylpentadiol, trimethylpentadiol monoisobutyrate, trimethylpentadiol diisobutyrate, and butylcarpitol are used.

In addition, the amount used is 20% of the acrylic acid resin.
It is desirable to keep it as small as possible.

Regarding the lower limit of the glass transition temperature, if it is lower than -40°C, the main skeleton of the resin may become too soft and it may be difficult to obtain sufficient mechanical strength even after crosslinking has progressed.
It is preferable to set the temperature to 0°C or higher, particularly -30°C or higher.

The cement composition of the present invention is produced by kneading the above-described aqueous emulsion of acrylic acid resin and cement together with fillers, pigments, antifoaming agents, and other additives as necessary.

Examples of the cement to be mixed with the aqueous emulsion include all known cements such as Portland cement, early strength cement, ultra early strength cement, alumina cement, jet cement, blast furnace cement, pozzolan cement, sulfate-resistant cement, and white Portland cement.

Filling materials are used as necessary, such as silica sand and crushed sand.

Blast furnace slag crushed sand 1 Input lightweight aggregate 3 River sand, sea sand, mountain sand, perlite calcium carbonate powder, asbestos, alkali-resistant glass fiber, steel fiber, carbon fiber.

It is appropriately selected from among fly ash, titanium oxide, iron ore sand, etc. depending on the purpose of construction. The antifoaming agent is used in an amount of 0 to 5% based on the aqueous emulsion, if necessary. This is effective in creating a dense cement hardened body. As the pigment, inorganic pigments such as Hengara, carbon black, etc. and commonly used organic pigments are used.

Regarding the mixing of the aqueous emulsion with cement, etc., there is no problem in applying the usual method of kneading and mixing cement. For example, a predetermined amount of aqueous emulsion and filler, etc., are added to cement, and this is mixed by hand using a portable electric mixer, paint dispersion mixer, mortar mixer, etc., or in some cases, by hand using a mortar spoon. By kneading, the desired cement composition can be obtained. In this case, the aqueous emulsion may be used by diluting it in advance with part or all of the kneading water added to the cement.

In addition, the mixing ratio of the aqueous emulsion to the cement is usually in the range of 1 to 200% based on the acrylic acid resin (solid content), and the mixing ratio of the aqueous emulsion to the cement is usually in the range of 1 to 200%. is selected. For example, when used for the purpose of improving only the adhesion performance of a hardened cement product, 1 to 40%, especially 5 to 25%, is sufficient and suitable, but when used for the purpose of giving further elasticity to the hardened cement product, 25% -200% is preferable, and 40-100% is more preferable. In this case, even if the aqueous emulsion is kneaded with cement and water, the crosslinking reaction does not proceed immediately at the temperature normally used, but proceeds simultaneously with the hydration reaction of the cement, forming an extremely convenient dense cement hardened structure. It is possible.

The cement composition thus obtained is particularly suitable for coating and finishing various adherend surfaces. For example, finishing mortar for concrete walls and floors of buildings, waterproof cement elastic cement coating materials, repair cement for old porcelain tile surfaces, and cement mortar paving for steel plate floors.

It can be widely used as a cement anti-rust coating material for steel products, a cement coating material for repairing exposed steel frames and reinforcing bars, and as a joint cement for concrete or porcelain tiles, etc., and exhibits excellent effects. In this case, the cement composition can be applied in the same manner as a normal cementitious finishing material. In other words, if the cement composition is in the form of cement mortar,
It can be applied with a metal trowel or wooden trowel. In the case of cement paint, a brush, spray gun, airless spray gun, etc. can be used. You can also mix it up softly and spread it on large floor surfaces using a tool commonly known as a dragonfly. The applied cement composition is cured by an air dry curing method, a moist air curing method, or the like. Once the film formation of the copolymer particles is completed, it can be cured by curing in water.

[Effect]

When the cement composition of the present invention is applied to the surface of an adherend as described above, the water in the cement composition is caused by the hydration reaction of the cement and the aggregation of moisture. Due to the so-called concentration effect, the acrylic acid resin particles, cement particles, filler particles, etc. approach each other and eventually come into close contact with each other. By the way, there are many cationic groups on the surface of the acrylic acid resin particles, so acrylic acid resin particles may be prepared by adding conventional cationic surfactants or cationic protective colloids, or by adding cationic surfactants or cationic protective colloids. It has strong cationic properties compared to copolymerized ethylenically unsaturated polymers (for example, alkylaminoethyl methacrylate). Therefore, acrylic acid resin particles and cement particles due to the above-mentioned concentration effect.

When the filler particles and the like approach and subsequently adhere to each other, the strongly cationic acrylic acid resin particles become anionically charged. It efficiently adsorbs and fuses to cement and filler adherends, which makes the distribution or arrangement of cement, filler, and resin particles uniform, and the effect of mixing acrylic acid resin becomes noticeable. I come to do it.

In conventional cement containing acrylic polymers, the acrylic polymer particles aggregate in the voids of the cement and filler and then fuse, resulting in uneven distribution of the cured polymer.
Although some degree of waterproofness was imparted, the effect on imparting elasticity and improving adhesiveness was small. On the other hand, according to the cement Vt composition of the present invention, not only the acrylic acid resin particles but also the cement particles, filler, etc. are uniformly distributed or arranged, so that the structure of the hardened cement product becomes dense and homogeneous. ,
Moreover, the uniformly distributed acrylic acid resin particles provide strong adhesion to adherends. and,
Adsorbs to cement particles, fillers, etc.

The functional groups on the surface of the fused acrylic resin particles cause a crosslinking reaction with the alkali of the cement, which not only forms a strong bond between the acrylic resin particles, but also bonds the resin particles, cement filler, and adherend. Strong adhesion is formed between the layers, and the adhesive strength is improved based on the uniform distribution of the acrylic acid resin particles.

Coupled with the effect of making the structure dense and homogenized, the hardened cement material becomes extremely firmly adhered to the adherend and becomes tough. In addition, the acrylic acid resin has excellent properties such as little deterioration or change in physical properties due to temperature changes, and is soft with a glass transition temperature of 10°C or less, so the cement cured product is , exhibits excellent elasticity not only in high temperature ranges but also in low temperature ranges.

〔Effect of the invention〕

The cement composition of the present invention uses an aqueous emulsion of an acrylic resin whose main component is the above-mentioned repeating unit and whose glass transition temperature is 10°C or less. It is possible to coat and finish adherends for which it was impossible to finish by coating, and to produce a hardened cement body that exhibits excellent elasticity not only in high-temperature regions but also in low-temperature regions. Furthermore, this cement composition does not cause cracks due to drying shrinkage during the drying and curing process, and the resulting cured product not only has extremely excellent adhesiveness and elasticity as described above, but also has a dense and homogeneous structure. Therefore, it has excellent waterproof properties, bending strength, tensile strength, impact resistance, and abrasion resistance.

Next, examples will be described together with comparative examples.

[Example 1] The following raw materials were charged into a hard glass emulsion polymerization reactor having an internal volume of 21 mm and equipped with an anchor type stirrer to prepare an aqueous emulsion of an acrylic acid resin.

(Composition of the aqueous solution charged into the flask at the beginning of 11 Polyoxyethylene nonylphenol ether (number of moles of ethylene oxide added: 20): 5 parts (weight, same below) Monobasic sodium phosphate = 0.5 parts Ammonium persulfate 20.5 parts Hydroxyethyl cellulose ( 2% aqueous solution viscosity IQcps): 3 parts industrial water
: 100 parts Total : 109 parts (2) Monomer mixture for polymerization Methyl methacrylate = 32 parts 2-ethylhexyl acrylate: 65m Dimethylaminopropyl methacrylate/epichlorohydrin adduct nitrate (90% aqueous solution); 3.3 The above aqueous solution was placed in a flask and heated to 75°C, and while maintaining that temperature, the above monomer mixture for polymerization was added dropwise evenly over 3 hours to carry out emulsion polymerization.
The reaction was completed by holding at 5°C for 1 hour. After cooling, the resulting aqueous acrylic acid resin emulsion was taken out. The physical properties of the obtained aqueous emulsion were as follows.

Solid concentration: 51% Viscosity (3Q゛c, BH type viscometer, same below): 350
0 cps The glass transition temperature (hereinafter referred to as rTgJ) of the acrylic acid resin (hereinafter referred to as "resin"): 14°C, pH = 2.2 Next, using the above aqueous emulsion, each raw material was blended as follows. It was mixed to make cement mortar.

Ordinary Portland cement = 100 parts Toyoura standard sand: 300 parts Aqueous emulsion = 39.2 parts (20 parts as solid content) Antifoaming agent (Nopco NXZ, San Nopco): 1 part Water: 45 parts The obtained cement mortar is commercially available. Semi-porcelain tile (dimensions 7.5X7
．． 5XQ, 5 parts m) Pour onto the glazed surface and add 4
．． A cement mortar layer of 5 x 4.5 x 0.5 cm was formed and air-dried and cured at 20°C for 3 weeks to form a hardened cement body.

[Comparative Example 1] Instead of the above aqueous emulsion, a commercially available acrylic ester copolymer emulsion CT (dimethylamine ethyl acrylate/2-ethylhexyl acrylate/methyl methacrylate copolymer) for cement mixing was used as a solid to the cement. It was used in a proportion of 20 parts. Other than that, a hardened cement layer was formed on the surface of a commercially available semi-porcelain tile in the same manner as in Example 1. The physical properties of the commercially available emulsion CT were as follows.

Solid content concentration 740% Viscosity: 150 cps Tg knee 5°C pH: 5.4 [Comparative Example 2] In place of the above aqueous emulsion, a commercially available acrylic ester copolymer emulsion US (acrylic acid/2-ethyl Hexyl acrylate/styrene copolymer) was used at a solid content of 20 parts based on the cement.

Other than that, a hardened cement layer was formed on the surface of a commercially available semi-porcelain tile in the same manner as in Example 1. The physical properties of the commercially available emulsion US were as follows.

Solid concentration: 58% Viscosity: Near 00 cps Tg: -25°C pH: 8.0 The adhesive strength of the hardened cement layers formed in the above Examples and Comparative Examples 1 and 2 was measured using a Kenken tensile tester. (The following measurements are also similar). The result is the first
Shown in the table.

Table 1 shows that the cement compositions of Examples can form a hardened cement layer that firmly adheres to the glaze surface, which is difficult to coat and finish with the cement compositions of Comparative Example 1.2. Recognize.

[Examples 2 to 11. Comparative Examples 3 and 4 parts The composition of the aqueous solution initially charged into the flask was changed as follows, and the composition of the monomer mixture for polymerization was changed to the following second composition.
I changed it as shown in the table. Other than that, an aqueous emulsion having physical properties shown in Table 2 was obtained in the same manner as in Example I.

(1) Composition of the aqueous solution initially charged into the flask Polyoxyethylene octylphenol ether (ethylene oxide addition mole B55): 5.0 parts Potassium persulfate 20.5 parts Monobasic potassium phosphate: 1.0 part Polyoxyethylene nonylphenol ether ( Number of moles of ethylene oxide added 15): 5.0 parts Industrial water: 100 parts Total: 111.5 parts In Table 2, the samples marked with an * are examples, starting from the smallest number. This corresponds to Examples 2 to 11 in this order. *Those not marked are comparative examples.

(Left below) Next, using the above aqueous emulsion, each raw material was mixed and kneaded in the following manner to prepare a cement mortar.

Early strength cement: 100 parts No. 6 silica sand: 100 parts No. 7 silica sand: 100 parts No. 8 silica sand: 100 parts Aqueous emulsion: Solid content 20 parts Commercial foaming agent
-0.5 parts Water: 50 parts The obtained cement mortar was mixed with the following 4, f! 4.5 x 4.5 x 0.
A 5 cm layer of cement mortar was formed and air-dried for 2 weeks at 20°C to form a hardened cement.

(Substrate) SS41 steel plate (6, OX9.OXo, 9cm) Lauan plywood (7,5X7.5Xo, 9cm) Semi-porcelain tile (
Glue to glaze surface, 7.5 x 7.5 Xo, 5CIn) Cement mortar board (7.0 x 7.0 x 2.0 cm)
The adhesive strength of the hardened cement layers formed in the above Examples and Comparative Examples was measured and shown in Table 3. However, 5
In addition to the above tests, for S41 steel plates, semi-porcelain tiles, and cement mortar plates, after one week of air-drying,
“Soak in room temperature water for 2 days, then 80°C for 2 days.
A cycling test was conducted for 5 cycles in which one cycle was "drying", and then the adhesive strength was measured after air-drying in a room for one week. The results are also shown in Table 3.

In Table 3, Nα14 is calculated by adding 5% dibutyl tucrate as a plasticizer to Kan 12 aqueous emulsion
These are the test results for mortar mixed with a substance added (based on the solid content) to lower the glass transition temperature to O'C.

(The following is a blank space) From the results in Table 3, it can be seen that the cement composition of the present invention exhibits excellent adhesion to all adherends, and also has good adhesion performance after cycling. On the contrary,
The cement composition (Sample Magnet 2) containing a resin that does not contain an alkali crosslinkable monomer used in the present invention has poor both initial adhesive strength and adhesive strength after cycling. Furthermore, even if the resin contains the same type of alkali crosslinkable monomer as used in this invention, if its glass transition temperature exceeds 10°C (sample patient 12
) has good initial adhesion, but the adhesion after the cycling test drops significantly and is of little practical use. However, even with such a copolymer, it is possible to improve the durable adhesiveness by adding a plasticizer to it and lowering the glass transition temperature to 10"C or less (Sample Description 19). ).In addition, although Sample Kan 13 uses a material with a glass transition temperature of 148°C, the performance was worse than that of the example using a material with a higher glass transition temperature, so acrylic was used. It can be seen that there is also a preferable lower limit of the glass transition temperature of the acid-based resin.

C Example 12. Comparative Examples 5 to 8) The composition of the monomer composition for polymerization was changed as shown in Table 4 below. Aqueous emulsions having physical properties shown in Table 4 were obtained in the same manner as in Examples 2 to 11 except for the above.

In Table 4, samples marked with an asterisk (*) are examples, and samples without marks are comparative examples.

(The following is a blank space) Next, using the obtained aqueous emulsion, the following (A
) and (B), two types of cement compositions were prepared and tested respectively.

(A) Cement mortar was prepared in the same manner as in Examples 2 to 11 with the same composition, and the adhesive strength to the surfaces of various adherends was measured and a cycling test was conducted in the same manner.

(B) 100 parts of white Portland cement, 50 parts of calcium carbonate powder, 100 parts of aqueous emulsion solid content,
A cement paint was prepared by thoroughly stirring and dispersing 0.2 parts of methyl cellulose, 3 parts of a reprint antifoaming agent, and an appropriate amount of water, and immediately poured it onto a smooth, releasable temporary surface to form a cement film with a thickness of 1 nm. After curing this at 20°C for one month, it was skewered on JISA6021 and a tensile test of the cement film was conducted to examine the physical properties.

The above test results are summarized in Table 5. In addition, the fifth
In the table, sample fb20 has the general formula (
Instead of using the cationic monomer in 4) or (5), a cationic surfactant is used to obtain a cationic emulsion, and the polymerization conditions are polyoxyethylene nonylphenol ether (non-polyoxyethylene nonylphenol ether). The same procedure was carried out except that lauryltrimethylamnium chloride (cationic surfactant) was used instead of (ionic surfactant), and the composition of the monomer mixture was 35 parts of methyl methacrylate and 65 parts of 2-ethylhexyl acrylate. The settings were the same as in Example 1.

(Left below) From the results in Table 5, it can be seen that the cement composition of the present invention has higher adhesion properties than the comparative cement composition containing a resin emulsion obtained by copolymerizing other crosslinking monomers. Not only does it have excellent overall adhesion to bodies, but it also has a good balance between tensile strength and elongation, and its temperature changes are small, so it has excellent physical properties (especially It can be seen that it exhibits elasticity). In particular, with respect to the adhesive strength after 5 cycles, while the comparative example significantly decreased, the adhesive strength of the present invention hardly changed or even improved, and there is a large difference between the two. This difference occurs because the hardened cement according to the present invention is highly elastic and follows temperature changes well in the cycling test, whereas the comparative example lacks elasticity and cannot follow temperature changes. It is thought to be from

[Example 13] As an aqueous solution and a monomer mixture for polymerization initially charged into a flask, those having the compositions shown below were used. An aqueous emulsion was produced in the same manner as in Example 1 except for the above. However, the reaction temperature was set to 70 to 75°C, and the monomer dropwise addition time was set to 4 hours.

(1) Composition of the aqueous solution initially charged into the flask Polyoxyethylene nonylphenol ether (ethylene oxide addition mole 1320): 6.0 parts Ammonium persulfate 20.4 parts Monobasic sodium phosphate: 0.5 parts Industrial water = 100 parts Total : 106.9 parts (2) Monomer mixture for polymerization Methyl methacrylate : 10 parts
Shin River Part 5 2-
Ethylhexyl acrylate: 42 parts Ethyl acrylate: 30 parts Dimethylaminopropyl methacrylamide epichlorohydrin adduct nitrate (70% aqueous solution): 4.3 parts
Total: 101.3 parts The physical properties of the obtained aqueous emulsion were as follows.

Solid content concentration: SO, Z% Viscosity: 480 cps Tg: -14°C pH: 3.1 Next, using the above aqueous emulsion, each raw material was blended as follows, and cement mortar (flow value 170).

Early strength cement, ': too Part No. 7 silica sand: 100 parts No. 6 silica sand: 100 parts No. 5 silica sand: 100 parts Aqueous emulsion: 30 parts as solid content Commercially available antifoaming agent
: 2 parts Water : Appropriate amount To repair an epoxy resin floor that has been installed for about 5 years, apply the obtained mortar over the entire surface to a thickness of 2 to 5 mm and finish it smooth with a metal mold. After air-drying for a week, a water-based floor paint (green) was applied with a brush, and the repair work was completed. The adhesive strength of mixed mortar to the epoxy resin surface was 8.4 kg/cJ after 7 days of age (immediately after air-drying).
(All materials were destroyed) and was extremely good.

Incidentally, for comparison, the adhesive strength to the epoxy resin floor surface was measured under the same conditions using the commercially available acrylic copolymer aqueous emulsion CT and US used in Example 1, but the adhesive strength was Okg for both. /cd.

[Example 14] As an aqueous solution and a monomer mixture for polymerization initially charged into a flask, those having the compositions shown below were used. An aqueous emulsion was produced in the same manner as in Example 1 except for the above.

(1) Composition of the aqueous solution initially charged into the flask Polyoxyethylene nonylphenol ether (number of moles of ethylene oxide added: 25) Nia, 0 parts Potassium persulfate: 0.6 parts Industrial water Nia 0 parts Total Nia 7.6 parts (2) Polymerization monomer mixture butyl methacrylate: 15 parts
Thin: 10 parts Ethyl acrylate: 25 parts Butyl acrylate: 45 parts Dimethylaminoethylmethacrylamide/epichlorohydrin adduct chloride (
90% water soluble i): 5.5 parts
Total: 100.5 parts The physical properties of the obtained aqueous emulsion were as follows.

Solid content concentration: 59.1% Viscosity: 1520 cps Tg knee 18”C pH: 2.3 Next, using the above water-based emulsion, mix each raw material as follows. value 200).

Early strength cement: 100 parts No. 7 silica sand: 100 parts Aqueous emulsion: 50 parts as solid content Commercial antifoaming agent
: 3 parts Water : Appropriate amount The obtained mortar was applied to the concave parts of the outdoor asphalt concrete surface with gold to repair the asphalt concrete surface to make it smooth. After air-drying for one week, a urethane resin flooring material was applied to a thickness of 5 fl to create a tennis court. When the finished condition was observed one year after completion, it was in good condition with no change at all, and the adhesion between the asphalt concrete surface hardened cement layer and the urethane resin flooring layer was extremely good.

By the way, for comparison, commercially available acrylic copolymer aqueous emulsions CT and US used in Example 1 were applied to the recesses of an outdoor asphalt concrete surface under the same conditions as above, smoothed, and then painted with urethane resin on the floor. I painted the wood. However, about 6 months later, CT and u
The hardened 52M cement layer absorbed water from the soil and swelled, creating unevenness on the urethane floor surface.

Claims (4)

[Claims] (1) A cement composition containing the following components A and B as main components. (A) having at least one of a repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3) as main components, An aqueous emulsion of acrylic acid resin with a glass transition temperature of 10°C or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・...(3) [In formulas (1) to (3), R is hydrogen or a methyl group, R_1 and R_2 are a methyl group or an ethyl group, and may be the same or different. R_3 is an alkyl group or a cycloalkyl group having 1 to 12 carbon atoms. A is -O- or -NH-, X is chlorine, bromine or iodine, and Y is an organic or inorganic anion. n is 2 or 3. ] (B) Cement. (2) The cement composition according to claim 1, wherein the acrylic acid resin has a glass transition temperature within the range of 0°C to -40°C. (3) Repeating unit represented by general formula (1) and general formula (
The cement composition according to claim 1 or 2, wherein at least one of the repeating units represented by 2) is set to 0.5 to 10% of the total acrylic resin based on the weight. (4) Any one of claims 1 to 3, wherein the proportion of component A used is set to be 1 to 200% by weight of component B based on the solid content of component A. The cement composition according to claim 1.