JPS5934670B2 - mortar composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to mortar compositions, and more particularly to mortar compositions containing an aqueous epoxy resin dispersion.

Conventional mortar compositions using cement as a binder tend to harden due to dryness and cause poor adhesion when applied to a dry surface, and increasing the amount of water to prevent this causes a decrease in strength and cracks due to curing shrinkage. Also, because it has a breathing property, it produces laitance, and when painting or adhering other objects thereon, it has the disadvantage that the original sufficient adhesive strength cannot be obtained unless the laitance is completely removed.

Furthermore, if it is used in a structure that requires waterproofing because it is not waterproof, it is necessary to perform complete waterproofing work before or after mortar construction, and the fluidity of the hydrated mixture is poor, making painting workability difficult, especially when spraying. It has many drawbacks such as poor painting workability.

In order to solve these drawbacks, some formulations add synthetic resin emulsions such as ethylene-vinyl acetate copolymer, acrylic resin, acrylic-styrene copolymer, and styrene-butadiene copolymer to the mortar composition. Although these are effective to some extent in improving the adhesion and flexibility (bending strength and tensile strength) of mortar, they lack the compressive strength and rigidity inherent to mortar, and are non-reactive and harden. If the emulsion is not completely dry, it will not form a film, so it will not be effective in a humid place.Furthermore, since these synthetic resin emulsions dry quickly, the surface of the mortar dries quickly and is difficult to re-trowel. There are problems such as poor workability, so it has not become widely used.

Mortar compositions using an aqueous epoxy resin dispersion have also been described in some literature, but in general, these compositions improve adhesion and flexibility, but the mortar is too sticky and cannot be troweled. The workability of troweling such as troweling is very poor, and the addition of epoxy resin water dispersion and hardening agent inhibits the hydration reaction of cement, resulting in slow curing of mortar and inferior mortar's original rigidity and strength. In addition, there is a drawback that the physical properties of the epoxy resin are extremely deteriorated after gelation, so it is hardly used as a mortar composition at present.

In addition, additives and compounding materials for the purpose of modifying cement include water reducing agents, air entraining agents, quick setting agents, coupling agents, antifoaming agents,
Many viscosity agents, anti-shrinkage agents, water retention agents, fibrous compounding materials, waxes, etc. have been developed and many are commercially available, but these have little effect on modifying mortar or are not effective for certain properties. Even if there is, most of them have advantages and disadvantages that adversely affect other properties, and at present no mortar composition has been created that solves all of the disadvantages of conventional mortars.

The present inventors have conducted various studies to improve these drawbacks, and as a result, we have developed an aqueous dispersion of epoxy resin with a softening point of 40 to 90°C for cement, aliphatic polyamines, alicyclic polyamines, and the like. It is one type or a mixture of two or more derivatives, and when mixed in the epoxy resin aqueous dispersion, the viscosity when the solid content (total amount of epoxy resin content and curing agent) is 25% is 60 seconds (+4 food cup). , 20°C) or less, the solid content of the mixture of both is 1 to 20%,
By adding 0.3 to 5% of one or a mixture of two or more of alkali metal salts selected from lithium, sodium, and potassium of melamine resin sulfonic acid as an additive, the synergistic effect of these can eliminate the drawbacks of conventional mortar. It was discovered that a mortar composition with excellent physical strength, adhesion, thin coating hardening, crack resistance, waterproofness, breathing resistance, and painting workability can be obtained by completely improving the above, and in order to complete the present invention. It's arrived.

Particularly, the present invention is a mortar composition containing an epoxy resin water dispersion, a hardening agent, cement, aggregate, and additives, wherein the epoxy resin of the epoxy resin water dispersion has a softening point of 40.
~90°C, the curing agent is at least one of aliphatic polyamines, alicyclic polyamines, and derivatives thereof, and the epoxy resin content and curing agent content of the mixture added to the epoxy resin aqueous dispersion are A mortar composition having a viscosity of 60 seconds (+4 fed cup, 20°C) or less when the total weight is 25% of the mixture, and the additive is an alkali metal salt of melamine resin sulfonic acid. .

The reason why such excellent performance was obtained is not clear, but among the various grades of epoxy resin ranging from liquids with relatively low viscosity to solids with high softening points, epoxy resins with softening points of 40 to 90°C By using an aqueous dispersion of an epoxy resin and the above-mentioned specific curing agent that has a relatively low viscosity when mixed with the water dispersion, the epoxy resin does not inhibit the water utilization reaction of the mortar and has good troweling workability. Water dispersions do not gel even when mixed with a hardening agent, or it takes a very long time to gel, so there is little change in physical properties depending on the time after mortar kneading until use. By adding melamine resin sulfonate, the amount of water in the cement can be significantly reduced, and since these are amine compounds and have very good affinity with the epoxy resin water dispersion, they have a synergistic effect and have excellent various properties. It is assumed that performance was obtained.

The epoxy resin of the epoxy resin aqueous dispersion used in the present invention has a softening point of 40 to 90°C, has two or more epoxy groups in its molecule, and is cured by reacting with the curing agent of the present invention at room temperature. If so, there are no particular restrictions on the type of epoxy resin, and all can be used.

However, epichlorohydrin-bisphenol A type epoxy resin is preferred from the viewpoint of versatility, price, etc. of the epoxy resin.

If the softening point of the epoxy resin is below 40℃, the mortar's troweling workability and curing speed will be significantly reduced, the original rigidity of the mortar will not be obtained, and the physical properties will change significantly depending on the time it takes to use the mortar after mixing. It is not desirable because it is large.

The reason for this is not clear, but because the epoxy resin's dispersion state is partially destroyed by physical action during mortar mixing, its softening point is low, and due to the effect of frictional heat, cement, aggregate, etc. It coats the surface and makes the mortar sticky, making it difficult to apply with a trowel. It also inhibits the hydration reaction of cement, and forms a waterproof film on the surface of cement particles as the epoxy resin hardens. It is assumed that this is because the water use response is interrupted.

If the softening point of the epoxy resin is 90°C or higher, the curing reactivity at room temperature will be very low, and when the epoxy resin is heated and melted to produce an aqueous dispersion, foaming will occur because the temperature is close to the boiling point of water. , which is undesirable because it tends to cause troubles such as boiling.

Epoxy resin aqueous dispersion is made by heating the epoxy resin to a temperature above its softening point to make it liquid, then adding an emulsifier, a small amount of protective colloid, an antifoaming agent, etc. as necessary, and then using a homogenizer or desilver while maintaining the temperature. It can be made by adding hot water to a large-scale stirrer and dispersing it in water.

It is also possible to dissolve the epoxy resin in an organic solvent in advance and then disperse it, but since the organic solvent has the effect of retarding the hardening of the cement, it is not preferable to use a large amount of the organic solvent (more than 3 parts relative to the cement).

The aliphatic polyamine used as a curing agent is an aliphatic compound having at least two amino groups and/or imino groups in the molecule that have an active hydrogen atom that reacts with an epoxy group at room temperature, such as diethylenetriamine, triethylenetetramine, and tetramine. Ethylenepentamine, pentaethylenehexamine, diethylaminepropylamine, hexamethylenediamine, trimethylhexamethylenediamine,
Alicyclic polyamines such as polyochirapropylene diamine and iminobishexylamine are alicyclic compounds having at least two or more amino groups and/or imino groups in the molecule that have active hydrogen atoms that react with epoxy groups at room temperature. For example, xylylenediamine, 3,9bis(3
-aminopropyl)-2,4,8,10tetraoxaspiro[(5,51undecane, N-aminoethylpiperazine, bis(4-aminocyclohexyl)methane, etc.). Monotylene oxide adducts of polyamines, epoxy resin adducts,
Modified aliphatic polyamines such as polyethylene polyamine modified products, modified alicyclic polyamines such as monoglycidyl ether adducts of alicyclic polyamines, epoxy resin adducts, acrylonitrile adducts, fatty acid glycidyl ester adducts, polyethylene polyamine-fatty acids, Examples include polyamide amines which are condensation reaction products such as polyethylene polyamine-dimer acid and xylylene diamine-dimer acid, and modified products thereof.

One or a mixture of two or more of these curing agents has a viscosity of 60 seconds (-#-4 Ford 20° C.) or less.

When the mixing viscosity is 60 seconds or more, the viscosity of the mortar becomes high, and the amount of water required to obtain a predetermined viscosity suitable for the work is large (this results in a decrease in physical properties, which is not preferable).

The required ratio of the curing agent to be mixed into the epoxy resin aqueous dispersion is not particularly limited in the case of epoxy resins since there is a wide allowable range in the amount of curing agent added, but the equivalent ratio is epoxy resin di-curing agent-0,6:1. It is preferably within the range of 4-1.4-0.6.

Further, the curing agent can be used as it is, or as an aqueous solution or dispersion.

The amount of the aqueous epoxy resin dispersion and curing agent of the present invention to be used is 1 to 20 parts, preferably 3 to 20 parts, per 100 parts by weight of cement (hereinafter weight is omitted) as a solid content of the mixture of the two.
If the amount used is less than 1 part, the desired reforming effect cannot be obtained, and if it is more than 20 parts, the inherent rigidity of cement mortar cannot be obtained, which is not preferable.

The additive melamine resin sulfonate is represented by the general formula, and one or a mixture of two or more of these is used in an amount of 0.2 to 4 parts, preferably 0.4 to 3 parts, per 100 parts of cement. use part.

These are made by sulfonating melamine formaldehyde resin obtained by reacting melamine and formaldehyde under alkaline conditions at 50 to 90°C, and adding lithium, sodium, and potassium carbonates, hydroxides, etc. to make sulfonates. It is a solid water-soluble resin, and is used in the form of a powder or an aqueous solution, in addition to the melamine resin sulfonate alone, as a composite with other substances such as methyl cellulose, hydroxyethyl cellulose, and sodium acrylate.

If the amount added is less than 0.2 parts, the desired water-reducing effect and synergistic effect with the epoxy resin cannot be obtained, and if it is more than 4 parts, the cured mortar becomes brittle and cracks are likely to occur, which is not preferable.

The cement used in the present invention is a hydraulic silicate calcareous cement, such as ordinary Portland cement, early strength Portland cement, ultra early strength Portland cement,
Examples include single cements such as moderate heat Portland cement and white cement, and mixed cements such as blast furnace cement, silica cement, and fly ash cement.
It can be used as a species or as a mixture of two or more.

Examples of aggregates include silica sand, river sand, crushed stone, crushed porcelain, crushed glass, glass peas, etc. The particle size of the aggregate should be 2 cities or less from the viewpoint of ease of thin application of mortar, and the water absorption of the aggregate. It is preferable to have as little as possible because the water/cement ratio becomes smaller and better physical strength is obtained.

In addition, if the aggregate is silica sand, river sand, or crushed stone, the composition is 5
Aggregates with a high i02 content are preferable because the physical strength of the aggregate itself is high.

The mixing ratio of these aggregates to cement is cement 1
0.5 to 6 parts, preferably 0.7 to 4 parts.

In addition to the melamine resin sulfonate, additives include antifoaming agents, foaming agents, setting accelerators, setting retarders, rust preventives, waterproofing agents, swelling agents, dispersants, etc., and are used as necessary. can do.

Other compounding materials that may be used as necessary include chopped strand glass fiber, short synthetic resin fiber, asbestos, pulp, glass flakes, mica powder, mica powder, and MI.
O (scaly iron oxide), crushed stone, talc, clay, wax, bituminous material, gypsum, fly ash, blast furnace slag powder-microsilica, etc. can be used as appropriate depending on the purpose.

The mortar composition of the present invention can be prepared by not only measuring and kneading each material at the time of use, but also using a solid material pre-mixed with cement, aggregate, solid additives, and compounding materials in a factory, and a water dispersion of epoxy resin. It is possible to use a set of curing agents and other liquid materials, and these materials are thoroughly kneaded with a mixer, concrete mixer, shovel, trowel, etc. until the whole is evenly mixed.
It can be applied by methods such as trowel application, spray application, brush application, and spatula application.

In addition, it has good paint workability, anti-breathing properties, and thin-coat curing properties, and the cured coating film has excellent physical strength, adhesion, crack resistance, and waterproof properties, so it can be used in water treatment plants, sewage treatment plants, septic tanks, etc.
Waterproofing and lining base material for digestion tanks, basements, subways, tunnel interiors, dams, pump rooms, etc., concrete joints, crack repair, waterproof reinforcement around pipes, blocks, A
It can be used for a wide range of purposes, such as joint material for LC boards and bricks, flooring and repair of factory floors, indoor floors, etc., and repair of defective parts such as concrete slabs, junkers, and uneven surfaces.

Next, the present invention will be specifically explained with reference to production examples and examples.

Parts and units in the examples are parts by weight and percent by weight, respectively.

However, the present invention is not limited to these manufacturing examples and examples.

Production Example 1 50 parts of Epomic R-302 (epichlorohydrin-bisphenol A type epoxy resin, softening point 75-85°C, manufactured by Mitsui Kanebo Epoxy ■) was heated and melted at 95°C, and polyoxine ethylene nonylphenyl ether (HLB) was melted by heating to 95°C.
= 16), add 0.2 parts of methyl cellulose, and add 46.8 parts of warm water while stirring with a homogenizer while maintaining the temperature.
of the mixture was gradually added to obtain an epoxy resin aqueous dispersion.

Production Example 2 50 parts of Epomic R-301 (epichlorohydrin-bisphenol A type epoxy resin, softening point 65-75°C, manufactured by Mitsui Kanebo Epoxy ■) was heated and melted at 90°C, and then mixed with epoxy resin water in the same manner as in Production Example 1. A dispersion was obtained.

Production Example 3 50 parts of Epomic R-300 (epichlorohydrin-bisphenol A epoxy resin, softening point 52-56°C, manufactured by Mitsui Kanebo Epoxy ■) was heated and melted at 75°C, and then mixed with epoxy resin water in the same manner as in Production Example 1. A dispersion was obtained.

Manufacturing example 4 Epomic R-3004z part, Epomic R-144 (
A mixed epoxy resin (softening point: 43°C) consisting of 8 parts of epichlorohydrin-bisphenol A type epoxy resin (liquid high viscosity, manufactured by Mitsui Kanebo Wepoxy ■) was heated and melted at 70°C, and the epoxy resin was prepared in the same manner as in Production Example 1. A water dispersion was obtained.

Production example 5 ADEKA epoxy resin EPX27 (bisphenol A side chain type epoxy resin, softening point 50°C, manufactured by Mudenka Kogyo ■) 5
0 part was heated and melted at 70° C., and the following procedure was repeated in the same manner as in Production Example 1 to obtain an epoxy resin aqueous dispersion.

Production example 6 Epicron 10], 0 (methyl epichlorohydrin-bisphenol A type epoxy resin, softening point 65-7
(manufactured by Dainippon Ink & Chemicals Co., Ltd.) was heated and melted at 90°C, and the same procedure as in Production Example 1 was repeated to obtain an epoxy resin aqueous dispersion.

Comparative production example 1 Epomic R-30036 parts, Epomic R-1441
Mixed epoxy resin (softening point 35°C) consisting of 4 parts at 60°C
℃, and to this was added 3 parts of polyoxyethylene nonylphenyl ether (HLB=16) and 0.5 parts of methyl cellulose.
2 parts of water was added thereto, and 46.8 parts of water was gradually added while stirring with a homogenizer to obtain an epoxy resin aqueous dispersion.

Comparative Production Example 2 450 parts of Epomic R-14 was heated to 50°C, and the same procedure as in Comparative Production Example 1 was carried out to obtain an epoxy resin aqueous dispersion.

Comparative Production Example 3 50 parts of Epomic R-140 (epichlorohydrin-bisphenol A type epoxy resin, liquid, manufactured by Mitsui Kanebo Eboxy ■) was heated to 30°C, and an epoxy resin aqueous dispersion was prepared in the same manner as in Comparative Production Example 1. Obtained.

Comparative manufacturing example 4 ADEKA epoxy resin EP4000 (bisphenol A
50 parts of side chain type epoxy resin (liquid, manufactured by Mudenka Kogyo ■) were heated to 30° C., and the same procedure as in Comparative Production Example 1 was carried out to obtain an epoxy resin aqueous dispersion.

Comparative Production Example 5 50 parts of Epiclon 5OO (methyl epichlorohydrin-bisphenol A type epoxy resin, liquid, manufactured by Dainippon Ink & Chemicals) was heated to 50°C, and the following procedure was carried out in the same manner as in Comparative Production Example 1 to prepare an epoxy resin aqueous dispersion. I got it.

Examples 1 to 7, Comparative Examples 1 to 6 Epoxy resin aqueous dispersion [Xenamide 4250C polyamide amine, manufactured by Henkel Japan ■] in the proportions shown in Table 1,
After stirring and mixing "Zenamide + 2000 (polyamide amine, made by Henkel Japan)" and water, add a mixture of ordinary Portland cement, silica sand No. 7, and melamine resin sulfonic acid sodium salt, and knead thoroughly until the whole is homogeneous. Examples 1 to 7 and Comparative Examples 2 to 60 mortar compositions were obtained.

In Comparative Example 1, a mixture of ordinary Portland cement and silica sand No. 7 was added to water and thoroughly kneaded in the same manner to obtain a mortar composition.

The viscosity (1:
4 food cups, 25°C) were as follows:

Example 7 43 seconds The test results for these mortar compositions are shown in Table 2.

Test method Breathing rate (section) * Measure the mass (Wo) of the specimen (70x70:x'2mm).

After completely removing the breathing layer on the surface of the specimen with a wire brush and cleaning the surface, the mass (W) is measured.

Breathing rate (person) - (Wo-wl) //Wo x 10
0 Thin paint curable Apply a thin coat to a thickness of 1 mrn on a flexible board and measure the pencil hardness of the paint film (20°C 173 R, H) Adhesion strength * JIS A 6911 (Cement thick spray material 4)
．． According to 6.

Compressive strength and bending strength * Based on JIS A 1172 (Strength test method for polymer cement mortar).

Water absorption rate * Dry the specimen (40 x 40 x 160 mm) at a temperature of 80 ± 2°C until it reaches a constant weight, and measure the mass (Wo).

Next, this was immersed in fresh water at a temperature of 20 ± 2°C, and
After the time has elapsed, take it out, quickly wipe each side with a compress, and immediately measure the mass (Wl).

Water absorption width - (Wl-wo)/Wo x 100 Water permeability * 6.4 of JIS A 6910 (multilayer pattern sprayed material)
by.

Size of specimen: 120 x 120 x 10 mm 20±2℃, humidity 60±1OL:
Test after storage in l).

As is clear from Table 2, the mortar compositions of the present invention (Examples 1 to 7) using an aqueous epoxy resin dispersion with a softening point of 40 to 90°C are different from each other using a liquid or low softening point epoxy resin. Compared to the comparative example, very good results were obtained in terms of troweling workability, thin coating curing properties, adhesion, physical strength, water absorption, and water permeability.

Moreover, almost no change in physical properties was observed depending on the time from kneading the mortar composition to use.

The mortar composition of Comparative Example 1 (Brain mortar) has a high breathing rate and tends to cause temporary setting, resulting in poor coating workability.When applied thinly, curing failure occurs due to dryout, and the hardness remains low even after 10 days. was below 6B.

Furthermore, the adhesiveness was poor, the water absorption rate and water permeability were very high, and poor results were obtained in other test items as well.

Examples 8 to 17, Comparative Examples 7 to 14 Examples 1 to 7 and Comparative Examples 1 to 6 at the blending ratios shown in Table 3.
Each material was mixed and kneaded thoroughly in the same manner as in the case of Example 8 to 17 and Comparative Examples 7 to 14 to obtain mortar compositions.

The viscosity (+4 food cup, 2°C) of the epoxy resin aqueous dispersion-curing agent mixture shown in Examples 15 to 17 and Comparative Example 11.12 when the solid content was 25% was as follows.

Example 1518 seconds Comparative example 11 Unmeasurable/'161
7 seconds 〃 12 Unmeasurable/' 17 23 seconds The test results of Examples 8 to 16 and Comparative Examples 7 to 12 are shown in Table 4.

As shown in Table 4, the mortar compositions of the present invention (Examples 8 to 17) gave very good results in all test items.

In a test regarding the amount of the epoxy resin aqueous dispersion-curing agent mixture used for cement, good results were obtained in both Examples 8 and 90, which were within the range of the present invention (sections 1 to 20), whereas the amount used was In Comparative Example 13 where the ratio was less than 1φ, almost no effect of addition was observed, and in Comparative Example 14 where the ratio was 20 or more, the hardness and compressive strength were poor and the original rigidity of the mortar could not be obtained.

Differences depending on the metal types of sodium, calicum, and lyticum in melamine resin sulfonate (Example 3, 10.11
) was hardly recognized.

In addition, in tests regarding the amount of melamine resin sulfonate added to cement, good results were obtained in Examples 12 to 14 within the range of the present invention (0.2 to 4%), whereas 0. In Comparative Example 8 with .2 or less, the results were not much different from Comparative Example 7 which did not contain it at all, and no effect of addition or synergistic effect with the epoxy resin was observed.On the other hand, when the amount added was 4 or more, Poor adhesive strength, bending strength, water absorption, and water permeability were obtained.

In the test regarding the type of curing agent, Example 15 whose viscosity was within the range of the present invention (+4 Ford cup, 60 seconds or less) when the solid content of the mixture with the epoxy resin aqueous dispersion was 25 cl)
In Comparative Examples 13 and 17, very good results were obtained in all cases, whereas in Comparative Examples 13 and 14, the epoxy resin aqueous dispersion-curing agent mixture had a high viscosity and strong stickiness.
Due to poor trowel release during trowel application, and a high water/cement ratio, results were obtained in which thin coating curing properties, adhesive strength, physical properties, water permeability, and water absorption were poor.

Examples 17-20 Examples 1-7 and Comparative Examples 2-6 with the blending ratios shown in Table 5
Each material was prepared in the same manner as in Example 1, and thoroughly kneaded to obtain mortar compositions of Examples 18 to 21.

The water absorption amounts of the silica sand and porcelain powder and the SiO2 content of the silica sand in this example, Examples 1 to 17, and Comparative Examples 1 to 14 were as follows.

Water absorption *I 5i02 content *2 porcelain powder (48-65 meshes) 23g 1 The test results of Examples 18 to 21 are shown in Table 6.

*1 Approximately 1007 of the aggregate is placed in a 500 cL glass beaker and dried at 100-110℃ until it reaches a constant weight.
Measure Wo).

Add 300 g of fresh water at a temperature of 20±2°C to this, stir well, and leave at the same temperature for 3 hours.

Then, use a standard mesh sieve 44μ (75X20, JIS
Z 8801) to remove excess water, and then measure the mass (Wl) of the aggregate.

Water absorption amount = W, -W.

*2 Based on JIS R2212 (chemical analysis method for firebricks).

As shown in Table 6, good results were obtained with the mortar composition of the present invention (Example 18) using general silica sand as the aggregate.

Examples 19 and 20 using Silica Sand Gourd No. 6 (Shimane Kodo) and Silica Sand FS No. 6 (Yamagata Kodo), which have lower water absorption and higher SiO□ content than general silica sand products, and Examples using porcelain powder as aggregates. In No. 21, even better results were obtained in terms of thin coating curability, compressive strength, water absorption, and water permeability.

Claims (1)

[Claims] 1. Epoxy resin water dispersion, curing agent, cement, aggregate,
A mortar composition containing an additive, wherein the epoxy resin of the epoxy resin water dispersion has a softening point of 40 to 90°C.
and the curing agent is at least one of aliphatic polyamines, alicyclic polyamines, and derivatives thereof, and the total of the epoxy resin content and the curing agent content of the mixture added to the epoxy resin aqueous dispersion is A mortar composition having a viscosity of 60 seconds (≠4 Ford cups, 20° C.) or less when the weight of the mixture is 25, and wherein the additive is an alkali metal salt of melamine resin sulfonic acid. 2. In claim 1 above, the mixture of an aqueous epoxy resin dispersion and a hardening agent has a solid content (total amount of epoxy resin content and hardening agent) of 1 to 100 parts by weight of cement. 20 parts by weight, and a mortar composition in which the above-mentioned additive is also 0.2 to 4 parts by weight based on 100 parts by weight of cement. 3. The mortar composition according to claim 1, wherein the epoxy resin is an epichlorohydrin-bisphenol A type epoxy resin. 4 In claim 1 above, the aggregate has a particle size of 2
A mortar composition comprising silica sand having a water absorption amount of 26 mm or less per 101 M of aggregate.