KR102504056B1 - Ductile Cementitious Concrete Containing Modified Waterborne Acrylic Polymer - Google Patents

Abstract

The present invention relates to acrylic ductile cement concrete (ADCC) that imparts ductility to conventional brittle or rigid cement concrete and, more specifically, to ADCC containing a modified water-soluble acrylic resin, manufactured by modifying a bisphenol A type epoxy resin with liquid polar rubber (butadiene rubber), fatty acid, silane components, and the like and then dropping the same into an acrylic copolymer emulsion resin containing ion-exchanged water. The ADCC containing the water-soluble modified acrylic resin according to the present invention comprises: a composition in which a water-soluble modified epoxy resin, which is a first agent, is dropped into a water-soluble modified acrylic resin, which is a second agent; cement powder; coarse aggregate; and fine aggregate, wherein the water-soluble modified epoxy resin, which is the first agent, is a water-soluble resin in which a bisphenol A-type or F-type epoxy resin, a carboxyl-terminated butadiene copolymer, a silane coupling agent, and an unsaturated fatty acid are simultaneously entrained, and the water-soluble modified acrylic resin, which is the second agent, is a water-soluble resin in which styrene, acrylonitrile, and an emulsifier are polymerized.

Description

Softened cement concrete containing water-soluble modified acrylic resin {Ductile Cementitious Concrete Containing Modified Waterborne Acrylic Polymer}

The present invention relates to softening cement concrete in which ductility is imparted to conventional brittle or rigid cement concrete, and more particularly, after modification of bisphenol A type epoxy resin with liquid polar rubber (butadiene rubber), fatty acids and silane components, It relates to softening cement concrete (Acrylic Ductile Cement Concrete; ADCC) containing a water-soluble modified acrylic resin prepared by dropping it into an acrylic copolymer emulsion resin containing ion-exchanged water.

Most road pavements are composed of organic asphalt concrete pavement (ascon) and inorganic concrete pavement. It has problems such as pollution generated during the production of organic asphalt road paving materials, generation of waste asphalt pollutants due to early damage due to lack of rigidity, frequent maintenance, and lack of sustainability in terms of environment because it is based on fossil fuels.

In the case of inorganic cement concrete road paving materials, long-term common performance is excellent due to the effect of developing excellent stiffness, but shrinkage cracks, reflection cracks, fatigue cracks and blow-up due to lack of flexibility or stress relieving ability against temperature changes As a result, there is a problem of enormous post-maintenance costs.

Cement concrete is characterized by deterioration in durability due to surface aging and neutralization caused by weather conditions and ultraviolet rays. Weathering resistance to aging refers to resistance to weather changes and exposure to ultraviolet rays, and it is a known fact that the weather resistance of polymer cement concrete (PCC) in conventional examples is superior to general cement concrete.

Existing thermoplastic or thermosetting polymers to improve the ability to respond to physical changes such as neutralization of cement concrete, drying shrinkage cracks, and blow-up, and to impart predetermined stress relaxation properties to physical properties such as plasticity and brittleness Polymer cement concrete using resin has some disadvantages of durability degradation due to the influence of ultraviolet rays and curing temperature, etc., but is widely used for emergency repairs.

On the other hand, the road pavement for road use is used as a road pavement material by regulating the thickness and physical performance based on the axle load of an 8.2-ton truck. In the case of organic asphalt road pavement, it is mostly used for the surface layer, and the minimum tensile strength must be maintained at 0.7 MPa or more to function as a road pavement material for the surface layer. there is

In the case of using rigid inorganic unreinforced cement concrete as a surface slab for road paving, only a flexural strength of 4.5 MPa or more is set as the mixing standard based on the age of 28 days, but when the quality standards of special materials are cited, the compression of the age of 28 days is generally Quality standards such as strength and splitting tensile strength (splitting tensile strength) must be satisfied.

In the case of materials used for emergency repair of road pavement, polyurethane-based ascon material has very poor adhesion performance because it does not have a chemical base that can adhere to the existing organic or inorganic road pavement that has deteriorated or oxidized. In the case of conventional materials in which latex is added to ultra-fast cement, which is an inorganic material, the strength expression varies greatly depending on the air temperature, and due to the addition of latex, many bubbles are generated during mixing, so there are many voids inside. Therefore, there is a problem of early damage to concrete due to the propagation of cracks or penetration of rainwater into pores in the future.

In the case of the previously disclosed technology, in the case of organic ascon, adhesion strength is expressed by mechanical bonding due to the adhesiveness of the asphalt binder, or in the case of inorganic cement concrete, hydrates are formed by the pozzolanic reaction of water, aggregate, and cement to obtain strength. has the characteristic of expressing

According to Korean Patent No. 10-1796932, which is a prior art, in order to impart elasticity, the mixing ratio of latex was set as an experimental variable while the ratio of latex to cement and water was fixed, and 5%, 10%, 15%, and 20% of cement were used. As a result of measuring the compressive strength, flexural strength, split tensile strength, etc. according to age, it was judged that the improvement due to the latex mixture was not remarkable in the case of compressive strength. In addition, in all cases, the flexural strength satisfied the 4-hour traffic opening design standard strength of 3.15 MPa or more, which can be referred to as the standard for traffic opening, and the split tensile strength (splitting tensile strength) also showed characteristics that satisfied the design standard strength. However, the characteristics of the stress relaxation ability of a specimen in which latex is mixed with cement paste, which is an inorganic material, are not disclosed.

In addition, Japanese Patent No. 2000-0064725 uses a curing agent as a base where chemically pre-bonded ketone meets water and amine dissociates to cause curing, and Korean Patent No. 2005-0133872 uses thermosetting polyurethane and isocyanate as a curing agent. is using

In addition, Korean Patent No. 10-0922137 uses an acrylic polymer emulsion that has already been condensed in the manufacturing process as an additive, Korean Patent No. 10-1045877 uses polystyrene as a subject, and Korean Patent No. 10-1160540 uses A general epoxy resin that does not undergo any denaturation process is used. In addition, US Patent No. 2014-0035353 utilizes a silane group without being chemically entrained in the high-molecular-modified epoxy.

Therefore, a one-component water-soluble modified acrylic resin prepared by dropping a base and a modified epoxy resin that induces curing of an epoxy main material into a reactive group containing a large number of unsaturated fatty acids by entraining unsaturated fatty acids without a separate curing agent into an acrylic copolymer resin is utilized. To disclose a softening cement concrete endowed with stress relieving ability.

Registered Patent Publication No. 10-1796932 (2017.11.07) Registered Patent Publication No. 10-0922137 (2009.10.09) Registered Patent Publication No. 10-1045877 (2011.06.27) Registered Patent Publication No. 10-1160540 (2012.06.21)

An object of the present invention is to secure physical performance and stress relaxation performance by injecting a modified polymer resin into a mixture of general cement or ultra-fast cement, aggregate and other admixtures. Here, the physical performance induces hydrogen bonding with a large amount of hydroxide (Hydroxyl Group) generated during the hydration reaction of inorganic cement concrete to additionally express early strength, and through this, it is possible to secure the durability performance required for concrete design. In addition, the role of the rubber component contained in the water-soluble modified acrylic resin gives the rigid cement concrete a stress relieving ability, so that it can flexibly respond to the drying contraction and expansion due to temperature change.

In addition, by adjusting the input amount of water-soluble modified acrylic resin to reduce the water-cement ratio of general cement or ultra-fast cement, unsaturation products are reduced, so it is possible to suppress cracks caused by internal air bubbles and relieve stress while satisfying design strength standards. Its purpose is to provide a softening cement concrete material endowed with the ability.

The softening cement concrete containing the water-soluble modified acrylic resin according to the present invention for achieving the above object is

A composition in which a water-soluble modified epoxy resin as a first agent is added dropwise to a water-soluble modified acrylic resin as a second agent; and cement powder; and coarse aggregate; And fine aggregate; including,

The water-soluble modified epoxy resin as the first agent is

A bisphenol A or F type epoxy resin;

A carboxyl-terminated butadiene copolymer;

A silane coupling agent;

It is a water-soluble resin in which unsaturated fatty acids are simultaneously entrained.

The water-soluble modified acrylic resin as the second agent is

with Stylen,

with acrylonitrile,

It is characterized in that the emulsifier is a polymerized water-soluble resin.

And the first agent, the water-soluble modified epoxy resin,

Based on 100 parts by weight of water-soluble modified epoxy resin

25 to 70 parts by weight of the bisphenol A-type or F-type epoxy resin;

1 to 5 parts by weight of the carboxyl-terminated butadiene copolymer;

1.0 to 2.5 parts by weight of the silane coupling agent;

20 to 60 parts by weight of the unsaturated fatty acids;

Characterized in that it comprises 60 to 80 parts by weight of ion-exchanged water,

The water-soluble modified acrylic resin as the second agent is

Based on 100 parts by weight of water-soluble modified acrylic resin

10 to 30 parts by weight of the styrene;

1 to 10 parts by weight of the acrylonitrile;

The emulsifier is 0.5 to 5 parts by weight,

Characterized in that it comprises 60 to 80 parts by weight of ion-exchanged water,

Components constituting the water-soluble modified epoxy resin as the first agent and components constituting the water-soluble modified acrylic resin as the second agent are mixed in a stirrer, and the stirrer is installed on a mounting table,

The mounting table has a bottom plate placed on the floor, a buffer plate disposed on the bottom plate and having the agitator placed thereon, a buffer spring interposed here and there between the bottom plate and the buffer plate to absorb shock applied to the buffer plate, and the buffer plate It includes an impact dispersing means for uniformly distributing the applied impact to the entire buffer plate,

The impact dispersing means includes a rotary plate rotatably provided on the bottom plate, a plurality of first inclined blocks provided on the rotary plate and having an inclined surface formed thereon, and a corresponding inclined surface provided on the buffer plate at a lower part contacting the inclined surface. A plurality of second slope blocks formed thereon, slide rails formed on both sides of the first slope block, and slide rollers provided on both sides of the second slope block and inserted into the slide rail to move along the slide rail It is characterized by including.

The cement concrete to which the modified polymer resin has additional stress relieving properties is alleviated the brittle fracture properties of the concrete, enables internal stress dissipation, effectively copes with drying shrinkage cracking, and can effectively cope with blow-drying cracks of concrete slabs. It can suppress the blow-up phenomenon, and it has the effect of improving the durability of the concrete mixture by strengthening the adhesion by hydrogen bonding between inorganic concrete and organic polymer in addition to the bonding force by the existing hydration and pozzolanic reaction.

In addition, when the softening cement concrete containing the water-soluble modified acrylic resin according to the present invention is used as an emergency repair material, it has good adhesion with existing inorganic concrete, so it is suitable for road or bridge concrete repair work, and drying shrinkage is reduced compared to general concrete. .

1 is a water-soluble modified epoxy resin as a first agent in which rubber, unsaturated acid and silane are crosslinked according to an embodiment of the present invention.
Figure 2 is a graph showing the chemical properties before and after modification of a modified resin by a Fourie Transform Infra-Red (FTIR) test according to an embodiment of the present invention.
Figure 3 is a photograph showing a DHR (Dynamic High Shear Rheometer) test apparatus and specimen used for ductility test of an inorganic cement mixture containing a one-component water-soluble modified epoxy-acrylic copolymer resin composition according to an embodiment of the present invention.
Figure 4 is a graph showing the ductility behavior of cement concrete specimens according to comparative examples and embodiments of the present invention in stress-displacement relationship.
Figure 5 is a graph showing the ductile behavior of cement concrete specimens according to comparative examples and embodiments of the present invention in terms of cyclic stress-displacement relationship.
Figure 6 is a four-point-beam fatigue test apparatus photographed on cement concrete specimens according to comparative examples and embodiments of the present invention.
Figure 7 is a four-point-beam fatigue life test result graph performed on cement concrete specimens according to comparative examples and embodiments of the present invention.
8 is a cyclic stress-strain result graph among the four-point-beam fatigue test results performed on cement concrete specimens according to comparative examples and embodiments of the present invention.
9 is a view showing an agitator installed on a mounting table.
10 is a perspective view of a mount according to the present invention;
Fig. 11 is an exploded perspective view of Fig. 10;
Fig. 12 is a sectional view of Fig. 10;

Hereinafter, the softening cement concrete containing the water-soluble modified acrylic resin according to the present invention will be described in more detail with reference to the drawings.

Prior to a more detailed description of the softening cement concrete containing the water-soluble modified acrylic resin according to the present invention,

Since the present invention can have various changes and various forms, the implementation examples (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to a specific form disclosed, and should be understood to include all modifications, equivalents, or substitutes included in the spirit and scope of the present invention.

In each drawing, the same reference numeral, in particular, the same number of tens and ones digits, or the same reference numerals having the same tens digit, ones digit, and alphabet indicate members having the same or similar functions, and unless otherwise specified, each of the drawings Members indicated by reference numerals may be understood as members conforming to these standards.

In addition, the components in each drawing are expressed in exaggeratedly large (or thick) small (or thin) or simplified expressions in size or thickness in consideration of convenience of understanding, etc., but the scope of protection of the present invention is thereby limited. It shouldn't be.

Terms used in this specification are only used to describe a specific embodiment (aspect, aspect, aspect) (or embodiment), and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as ~comprising~ or ~consisting of are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

The softened cement concrete containing the water-soluble modified acrylic resin according to the present invention includes a composition in which a water-soluble modified epoxy resin as a first agent is added dropwise to a water-soluble modified acrylic resin as a second agent, cement powder, and coarse aggregate and fine aggregate.

Epoxy resin, which is a type of thermosetting polymer, is widely used in the construction and civil engineering fields because it has excellent adhesiveness, chemical resistance, heat resistance and mechanical properties compared to other types of polymers. However, the conventional epoxy resin is characterized in that the main agent and the hardener are cured only when the main agent and the hardener are mixed in a predetermined ratio in a two-component type. Therefore, since the use of a curing agent is inevitable to develop strength after attachment, drying, and curing, the complexity of mixing and using it, and the high cost of materials required for non-volatile components of 50% or more to exhibit excellent performance are known as disadvantages. .

In the case of the modified polymer resin of the present invention, that is, the modified hydrophilic epoxy resin, an unsaturated fatty acid is entrained without a separate curing agent, and a large number of reactive groups included in the unsaturated fatty acid, that is, a carboxyl group (-COOH), a carbon double bond (C=C ) not only utilizes a base that induces hardening of the epoxy subject by reacting with oxygen in the air and hydroxyl groups generated in large amounts during cement hydration, but also, as known in the prior art, It is characterized in that additional curing base is expressed by a ring-opening hydrogen bond reaction between an alkali hydroxide hydroxyl group (Hydroxyl Radical, -OH) and an epoxy group in a modified epoxy molecule.

■ Description of the chemical composition of the first agent, one-component water-soluble modified epoxy resin

The conventional technology using only one-component or two-component bisphenol A type unmodified epoxy resin similar to the present invention as an attachment material is difficult to properly control the pot life required for curing at the time of attachment, and resistance to cracking at low temperatures and stress Mitigation performance and the like have not been adequately evaluated. Chemical Formula 1 shows the molecular structure of unmodified bisphenol A-type epoxy, which has been mostly used for construction up to now. Overall, it has various characteristics, but brittleness, damage due to impact, and lack of flexibility due to temperature difference are the biggest problems of the prior art.

Therefore, it is necessary to impart physical properties, especially elastic properties, by entraining a rubber component in the esterification process and an acrylic copolymer in the condensation polymerization process to the reactants of Chemical Formula 1, and improving adhesion performance by inducing organic/inorganic reactions. For this purpose, it is necessary to apply the modification process such as silane treatment to the epoxy subject.

In addition, without using a separate curing agent, an unsaturated fatty acid having a carbon double bond and a carboxyl reactive group in the molecule is introduced to bond with air in the atmosphere or in the mixture, and water is added dropwise to form a one-component hydrophilic modification suitable for inorganic concrete. The purpose is to develop an epoxy polymer resin.

The hydraulic one-component resin composition according to the present invention is intended to be applied to a concrete mixture by using the drying performance of an acrylic resin and the moisture resistance, high adhesion, and granularity of an epoxy resin, and the application temperature range of the resin for concrete. is 5 to 120 ° C., the polymerization process of the resin is non-volatile, bubbles do not occur during reaction, and have very low shrinkage characteristics during curing.

In the present invention, an epoxy resin modified with fatty acid, rubber component, silane, etc. is used together with an emulsified acrylic resin to enhance elasticity and adhesion performance, and at the same time, it is an eco-friendly curing method that does not require a curing agent using oxygen in the air. It relates to softening cement concrete incorporating water-soluble modified epoxy and acrylic.

The rubber-modified and silane-treated epoxy resin for natural drying includes a bisphenol A epoxy resin, a carboxyl terminal rubber, a silane coupling agent, and an unsaturated fatty acid as non-volatile components.

In one embodiment of the present invention, the bisphenol A type epoxy resin may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

n is an integer from 0 to 30;

The bisphenol A or F-type epoxy resin is preferably included in an amount of 25 to 70% by weight based on 100% by weight of the rubber and silane-treated epoxy resin. If the content is less than 25% by weight, chemical resistance, solvent resistance, corrosion resistance, etc. may deteriorate, and if it exceeds 70% by weight, elasticity, adhesion, impact resistance, etc. may decrease, and natural drying, which is a characteristic of one-component resin, may be delayed. can

In one embodiment of the present invention, the carboxyl-terminated butadiene rubber copolymer may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

R' is a C ₁ -C ₁₀ alkyl or aryl group;

p and q are integers from 1 to 20;

m is an integer from 1 to 20;

As used herein, the C ₁ -C ₁₀ alkyl group refers to a straight-chain or branched monovalent hydrocarbon having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and the like, but are not limited thereto.

Aryl groups as used herein include both aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a simple or fused ring type consisting of 5 to 15 pentagons, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur or nitrogen. Representative examples of aryl groups include phenyl, naphthyl, pyridinyl, furanyl, thioph ennnnnyl, indolyl, quinolinyl, imidazolelinyl ), oxazolyl, thiazolyl, tetrahydronaphthyl, etc., but are not limited thereto.

The carboxyl-terminated butadiene rubber copolymer is preferably included in an amount of 1 to 5% by weight based on 100% by weight of the rubber-modified and silanized epoxy resin. If the content is less than 1% by weight, elasticity, adhesiveness, impact resistance, etc. may deteriorate, and if it exceeds 5% by weight, problems such as deterioration in emulsification performance, increase in foaming, increase in brittleness, and deterioration in adhesion performance due to the increase in unsaturated rubber components may occur. may occur.

In one embodiment of the present invention, the unsaturated acid may be a compound represented by Formula 3 below.

[Formula 3]

In Formula 3,

n is an integer from 1 to 10;

As the fatty acid used in the present invention, dimer acid, linoleic acid, palmitic acid, stearic acid, lauric acid, soybean oil fatty acid, castor oil fatty acid, and derivatives thereof may be used alone or in combination of two or more, but are not necessarily limited thereto. . Preferably, dimer acid, linoleic acid, palmitic acid, stearic acid and soybean oil fatty acids are used alone or in combination of two or more. As the unsaturated fatty acid introduced into the epoxy resin, a fatty acid having an iodine value of 110 to 180, preferably 110 to 150 is used. If the iodine value of the fatty acid is 150 or more, there is a risk of yellowing due to oxidation in the coating film.

The unsaturated fatty acid is preferably included in an amount of 20 to 60% by weight based on 100% by weight of the epoxy resin. If the content is less than 20% by weight, flexibility, drying properties, etc. may be reduced due to a decrease in the curing reaction, and if it is greater than 60% by weight, brittleness is increased due to excessive unsaturated components, or the drying time is greatly delayed due to an excessively high acid value. Or, the decrease in strength, chemical resistance, solvent resistance, corrosion resistance, etc. may decrease due to the increase in the amount of fine pores in the inorganic mixture.

In one embodiment of the present invention, the epoxy group of the bisphenol A or F-type epoxy resin of Chemical Formula 1 reacts with the rubber and fatty acid of Chemical Formulas 2 and 3 to form an epoxy resin capable of natural drying with improved toughness and elasticity, The epoxy resin may be represented by, for example, a compound represented by the following formula (4).

As shown in Formula 4, the epoxy block maintains its own domain while the acrylic and polybutadiene blocks constitute an elastic body area. In the case of fatty acids, carbon double bonds and carboxyl reactive groups react with oxygen in the air or in the composition to be cured. Such a polymer plays a role of maintaining physical properties such as stretching or elastic recovery while maintaining its own space according to external force within the molecule.

Since the space in the molecule is confined by the epoxy phase, which is the main component, when force is applied to the segmented copolymer (Grafrt Copolymer) in this modified epoxy with a special molecular structure, a portion of the energy is taken by the elastic rubber phase, polybutadiene and acryl. There are characteristics that make it happen. Therefore, the polybutadiene and acrylic copolymer imparts rubber elasticity that epoxy does not have before modification, and consequently imparts elasticity recovery characteristics to the modified composition.

[Formula 4]

In the case of the natural drying type curable epoxy resin, it not only maintains excellent mechanical properties (adhesive strength, oxidative stability, chemical stability, etc.) of the epoxy resin itself, but also contains 1 to 5% by weight of carboxyl-terminated butadiene air in the epoxy resin having brittle properties. By cross-linking the composite, it is modified into an epoxy resin having rubber properties, and after performing a curing step, it has excellent elasticity and exhibits more flexible physical properties at low temperatures.

In one embodiment of the present invention, the silane coupling agent includes a reactive group (-Y) that reacts with an organic material and an alkoxy group (-OR) that reacts with an inorganic material, and may be a compound represented by Formula 5 below.

[Formula 5]

In Formula 5,

R is hydrogen or a C ₁ -C ₄ alkyl group;

Y is an epoxy group, amino or C ₂ -C ₄ alkenyl group, preferably an epoxy group, amino or vinyl.

In the present specification, C ₁ -C ₄ alkyl group means a straight-chain or branched hydrocarbon having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl , t-butyl, and the like, but are not limited thereto.

As used herein, the C ₂ -C ₄ alkenyl group refers to a straight-chain or branched unsaturated hydrocarbon having 2 to 4 carbon atoms and having at least one carbon-carbon double bond, such as vinyl and propenyl. , butenyl, etc. are included, but are not limited thereto.

The C ₁ -C ₁₀ alkyl group, aryl group, C ₁ -C ₄ alkyl group and C ₂ -C ₄ alkenyl group have one or more hydrogens in the C ₁ -C ₅ alkyl group, C ₂ -C ₆ Alkenyl group, C ₂ -C ₆ alkynyl group, C3-C10 cycloalkyl group, C ₃ -C ₁₀ heterocycloalkyl group, C ₃ -C ₁₀ heterocycloalkyloxy, C ₁ -C ₅ haloalkyl group, C ₁ -C ₅ alkoxy group, C ₁ -C ₅ thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro, etc. can be replaced with

The silane coupling agent may be included in an amount of 1.0 to 2.5 parts by weight based on 100 parts by weight of the total resin of the ion exchange water drop-modified epoxy resin. If the content is less than 1.0 parts by weight, organic/inorganic reaction may be reduced, adhesion, heat resistance, etc. may be reduced, and if it is more than 2.5 parts by weight, unsaturated components may be excessive or flexibility may be deteriorated due to overreaction.

The silane coupling agent contains both a reactive group (-Y) that reacts with organic materials and an alkoxy group (-OR) that reacts with inorganic materials in the compound, and reacts with moisture to form a silanol group. , As shown in the following Reaction Scheme 1, the adhesion strength on the surface of the object to be attached is expressed due to the hydrogen bond or chemical bond between the hydroxyl group (-OH) present in the silanol group and the hydroxyl group on the surface of the object to be attached, which is an organic or inorganic material.

When the surface of the road pavement is made of an organic material, it has excellent compatibility between the modified epoxy resin and the organic material, thereby enhancing adhesion performance through a reaction between the organic compound of the resin or oil component in the organic material. Accordingly, the silane coupling agent may combine with an inorganic material to form an organic/inorganic bond, and bond with an organic material to form an organic/organic bond, thereby enhancing adhesion.

[Scheme 1]

The silane reactive group at the end of Scheme 1 develops adhesion strength by forming hydrogen bonds with hydroxyl groups of organic or inorganic molecules on the surface to be attached.

In one embodiment of the present invention, the epoxy resin in which the rubber, unsaturated fatty acid, and silane are crosslinked may be represented by, for example, a compound represented by Formula 6 below.

[Formula 6]

In Formula 6,

R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are hydrogen or C ₁ -C ₄ alkyl groups, and n is an integer from 0 to 30.

As shown in Chemical Formula 6, the first composition is prepared by dropping the first modified epoxy resin into ion-exchanged water, and then the first composition is added dropwise to the water-soluble emulsion acrylic resin synthesized as follows to obtain the final one-component water-soluble modified acrylic resin. A composition was obtained.

■ Description of the chemical composition of the second agent, water-soluble emulsified acrylic resin

In one embodiment of the present invention, the acrylic acid used in the synthesis of the water-soluble emulsified acrylic resin may be a compound represented by the following formula (7).

[Formula 7]

Acrylonitrile and methyl methacrylate copolymer, n is an integer from 1 to 20.

As the acrylic monomer used in the present invention, acrylic acid, methacrylic acid, styrene, pmarinic acid, methyl methacrylate, isobutyl acrylate, and derivatives thereof may be used alone or in combination of two or more, but are not necessarily limited thereto. no. Preferably, acrylic acid and isobutyl acrylate are used alone or in combination of two or more.

The styrene is preferably included in an amount of 10 to 30% by weight based on 100% by weight of the emulsified acrylic resin. If the content is less than 10% by weight, strength and drying performance may deteriorate, and if it exceeds 30% by weight, cracks may occur due to a decrease in tensile strength.

The acrylonitrile is preferably included in an amount of 1 to 10% by weight based on 100% by weight of the emulsified acrylic resin. If the content is less than 1% by weight, tensile strength, etc. may be lowered, and if it is more than 10% by weight, yellowing may occur on the concrete surface.

The emulsifier may contain one or more of a nonionic emulsifier and an anionic emulsifier, and the emulsifier may include polyoxyethylene stearyl ether and sodium dodecyl sulfate. The emulsifier is preferably included in an amount of 0.5 to 5% by weight based on 100% by weight of the acrylic resin. If the content is less than 0.5% by weight, it may be difficult to dissolve water, and if it is more than 5% by weight, water resistance may be deteriorated.

The water-soluble emulsified acrylic resin is preferably included in an amount of 70 to 90% by weight based on 100% by weight of the water-soluble acrylic-epoxy resin. If the content is less than 70% by weight, flowability (slump) may be reduced, and if it is greater than 90% by weight, ductility may be reduced and flexural strength may be reduced.

Hereinafter, the manufacturing process of the modified epoxy resin, which is the first agent of the present invention, is the resin section Example 1-1, and the water-soluble emulsified acrylic resin for dropping the first modified epoxy resin is specified and described as Example 1-2. do.

[Resin section Example 1-1: First agent water-soluble modified epoxy synthesis]

1000g of bisphenol A type epoxy resin (epoxy equivalent 475g/eq, product name: KER-3001, Kumho P&B Chemicals), 70g of butadiene rubber, and 850g of soybean oil fatty acid were added to a four-neck round flask (1L) equipped with a thermometer, condenser, and stirrer. After that, the temperature was slowly raised to 200 ~ 210 ℃. The condensation reaction was performed while maintaining the temperature of 200 to 210 ° C. at 200 rpm with agitation, and the reaction was terminated when the temperature reached 200 rpm to prepare a rubber fatty acid-modified epoxy resin. The acid value of the prepared modified epoxy resin was 8 mgKOH/g, and the epoxy group content was 50 mmol/kg.

After cooling the temperature of the flask containing the rubber fatty acid-modified epoxy resin to 120 ° C., 5 g of a silane coupling agent was added dropwise and reacted to prepare a silane coupling agent-introduced rubber and a fatty acid-modified epoxy resin. The epoxy equivalent of the prepared silane introduction-modified epoxy resin was 50,000 g/eq, and the viscosity was 18,500 cps.

Next, 110 g of triethanolamine and ion-exchanged water were added dropwise to the modified epoxy resin cooled to 70 ° C to emulsify. A one-component fatty acid-modified water-soluble modified epoxy resin having a weight percent of the resin) was obtained.

[Resin Section Example 1-2: Second Agent Water-soluble Emulsified Acrylic Resin Synthesis]

180g of potassium persulfate aqueous solution, 100g of ion-exchanged water, and 12g of sodium dodecylsulfate were added to a 4-necked round flask (1L) equipped with a thermometer, condenser, and stirrer, and the temperature was raised to 70℃, followed by 120g of styrene, 15g of acrylic acid, A mixture of 20 g of acrylonitrile and 110 g of butyl acrylate ester is uniformly added at 90 ° C for 5 hours

When the dropwise addition is completed, after maintaining the reaction for 6 hours, 1 g of potassium persulfate aqueous solution as a polymerization initiator is added, reacted for 1 hour, cooled to 60 ° C, and neutralized with triethanolamine or ammonia. At this time, the solid content of the emulsified acrylic resin is 50%, the viscosity is 100cps, and the pH is 9.1.

When cooled to 60 ° C., 80 g of the water-soluble modified epoxy resin prepared in Example 1-1 was added to the resin powder, stirred for 1 hour, and then cooled to 40 ° C.

At this time, the viscosity of the final resin is 50 cps (25 ℃), and the non-volatile content is 47.5%.

The physical properties of conventional waterborne polymer cement concrete (WPCC) vary depending on the water-cement ratio, aggregate-cement ratio, and polymer-cement ratio, but the main strength characteristics of WPCC are governed by the polymer-cement ratio. do.

In the present invention, the polymer-cement ratio is expressed as the weight ratio of the non-volatile matter (solid content) in the liquid polymer to which water is added dropwise to cement. At this time, the polymer (non-volatile content)-cement ratio can be adjusted within 5 to 40 parts by weight. It is desirable to carry out

The optimal polymer (non-volatile content)-cement ratio that improves tensile and flexural strength, compressive strength, neutralization resistance, adhesion, watertightness (waterproof performance), chemical resistance, abrasion resistance, and impact resistance within the above range must be determined.

At this time, when calculating the water-cement ratio (Water / Cement), it is necessary to determine the appropriate W / C by adding the amount of the loaded water to the water ratio, and usually maintain 30 to 50% of W / C to secure the slump and flow of WPCC It is desirable to do this, but it is desirable to make it as small as possible in order to secure the required strength.

Although it varies greatly depending on the curing conditions of WPCC, the highest strength can be obtained by initially performing underwater or wet curing and then air-drying curing. Curing in water promotes the hydration reaction of cement and the hardening reaction of polymer, and after drying, the network structure of polymer is sufficiently formed to express the effect.

In this case, when water is dropped and W/C is maintained at 40% or more, even if water or wet curing is omitted, the required strength can be expressed by dry curing, so in the case of the present invention, the initial water-cement ratio It is characterized in that air-curing, that is, air exposure curing, is carried out after maintaining pot life for at least 15 minutes without externally supplying water to maintain a wet state by maintaining it at a high level of 40% or more.

When the modified polymer is added dropwise to ion-exchanged water to initiate the final liquid water-soluble acrylic resin, when used as an admixture for cement concrete for road paving, the water-cement ratio prescribed in the specification is applied mutatis mutandis, but 100 parts by weight of the cement concrete mixture for road paving It is preferable to include 5 to 25 parts by weight of a water-soluble modified acrylic resin with respect to.

When used as an admixture for super-fast-setting cement concrete for emergency repair, the water-cement ratio prescribed in the specification is applied, but it is preferable to include 5 to 30 parts by weight of water-soluble modified acrylic resin based on 100 parts by weight of super-fast-setting cement concrete mixture. .

Here, regulated set cement refers to cement whose setting and hardening time can be arbitrarily changed, and is also called jet cement. Since the strength development is very fast, the compressive strength reaches about 100 ~ 200kg/cm ² 2 to 3 hours after adding water, so the formwork can be removed quickly, and even after 400kg/cm ² per day, the conventional It shows stable strength enhancement like crude steel and ultra-hard cement, so it can be used for urgent construction, motive construction, cement secondary products, shotcrete, and grout. In addition, super-fast-setting cement has, first, a short setting time and high heat generation during hardening. Second, it exerts great intensity in 2-3 hours. Third, there is no transition phenomenon like alumina cement. Fourth, it is necessary to be careful not to mix and use with Portland cement. In addition, ultra-fast-setting cement contains a large amount of 3CaO·3Al ₂ O ₃ ·CaSO ₄ that has high hydration activity and produces stable hydrates that do not exist in ordinary Portland cement. It is characterized in that it expresses high strength within several hours by generating calcium sulfoaluminate hydrate of high sulfate to form. In addition, this hydrate is continuously produced even after 1 day, and the structure of the hardened body becomes more dense and the strength expression is continuously improved by the gel-phase CSH hydrate produced by the hydration reaction of C ₃ S and C ₂ S present in ordinary cement. have a characteristic

The one-component water-soluble modified acrylic resin is preferably a resin containing 10 to 40 parts by weight of non-volatile matter in the case of cement concrete for road paving and ultra-fast cement concrete for emergency repair, based on the total weight of 100 parts by weight of the final composition loaded.

If the content of the liquid water-soluble modified acrylic resin is less than 5% by weight based on 100 parts by weight of the cement concrete mixture, drying performance may be greatly reduced after mixing with other compositions, and work performance and strength may be reduced. Exceeding 30% by weight In this case, the degree of crosslinking may increase, resulting in cracking, and the high ratio of unsaturated resin may hinder the hydration reaction of concrete, which may reduce the effect of developing strength.

Hereinafter, the present invention will be described in detail with examples in Table 1. However, the scope of the present invention is not limited by the examples.

division Psalm classification Water-soluble polymer content Comparative Example 1 Normal cement concrete (no additives) 0 Comparative Example 2 Latex-containing concrete (SB latex) 20 to 40 parts by weight Example Water-soluble modified acrylic resin concrete of the present invention 10 to 30 parts by weight

■ Indoor mixture test results (FTIR, DHR, and strength test)

[FTIR-chemical change test before and after denaturation]

The degree of modification of the modified resin of the present invention was verified as shown in FIG. 2 through a Fourie Transform Infra-Red (FTIR) test.

As shown in the above test results, it can be seen that the component characteristics before and after modification are very different. In particular, in the case of the graph shown above, a high peak due to fatty acid modification at Wavenumber 450 ~ 550 cm ^-1 and a strong peak at 1639 cm ^-1 A strong peak due to polymerization of rubber and acrylic near the carbon double bond peak, 3338 cm ^-1 can be confirmed.

[Ductile behavior characteristics-dynamic rheology test: Dynamic Shear Rheometer test]

The ductility of the inorganic cement mixture containing the modified polymer of the present invention, that is, the one-component water-soluble modified epoxy-acrylic copolymer resin, was tested.

Figure 3 is a photograph showing a DHR (Dynamic High Shear Rheometer) test apparatus and specimen used for the ductility test of the inorganic cement mixture containing the modified polymer, that is, the one-component water-soluble modified epoxy-acrylic copolymer resin, according to an embodiment of the present invention. am. It was verified by the DHR (Dynamic High Shear Rheometer) test as shown in FIG. 4 .

4 is a graph showing the ductility behavior of cement concrete specimens according to Comparative Examples and Examples of the present invention in terms of stress-displacement relationship, and FIG. 5 is a graph showing the ductility behavior of cement concrete specimens according to Comparative Examples and Examples of the present invention It is a graph showing cyclic stress-displacement relationship.

Referring to FIG. 4, the graph shows the stress-displacement relationship when the maximum load is displayed, and the slope of the comparative example-additive-free specimen is greater than that of the comparative 10% SB latex and the examples, indicating that the ductility is low and the brittleness is high. could

In addition, referring to FIG. 5, in the case of Comparative Example-no additive, the area in the load-displacement curve is very small, and it can be seen that stress relaxation hardly occurs during about 880 stress-displacement cycles. On the other hand, in the case of the conventional SB latex comparative example , Although some stress relief occurs due to the role of the latex rubber resin, in the case of the present invention containing a water-soluble acrylic resin with ion exchange water dropped (optimal content 10% by weight relative to the weight of cement), the maximum load is 500,000Pa It can be seen that the area in the stress-strain curve is relatively large while maintaining the stress relaxation behavior.

That is, as a result of the dynamic high shear rheology test as shown in FIGS. 4 and 5 for verifying the ductility effect of softened cement concrete, in the case of the comparative example-no additives, the elastic body behavior without dissipation of strain energy, In the example, while maintaining the same maximum load of 500,000 Pa, the tensile strain generated in the specimen is elongated by about 10 times to 0.15% when the unreinforced specimen is 0.015%, and the internal area of the cyclic load-displacement curve is relatively and the effect of stress relaxation ability was expressed to the maximum.

[strength test]

The physical properties of the inorganic cement mixture containing the one-component water-soluble modified epoxy-acrylic copolymer resin of the present invention were tested for flexural strength, compressive strength, and adhesion strength by combining Comparative Examples and Examples shown in Table 2 below. The test specimen for strength test was conducted on cement concrete, and in the case of the comparative example, a softened cement concrete mixture specimen incorporating a general cement mixture, a conventional Styrene-Butadiene (SB) latex polymer, and a water-soluble modified acrylic resin of the present invention was used as the target, In the case of Examples, the weight part of the water-soluble acrylic resin of the present invention was varied.

In the case of cement concrete specimens, the cement, fine aggregate, and coarse aggregate amounts were fixed, and the water and resin contents were added to prepare the specimens. Here, the fine aggregate refers to the aggregate that passes all of the 10mm sieve specified in the standard sieve, passes almost all of the 4.76mm sieve, and mostly remains in the 0.074mm sieve, and generally refers to those with a particle size of 5mm or less. On the other hand, the Ministry of Land, Transport and Maritime Affairs standard construction specifications define aggregates that pass through all 10mm sieves and pass 85% or more of 5mm sieves by weight. For this reason, a margin of about 15% was set. Coarse aggregate refers to aggregate with a particle size of 5 mm or more, but in the above specification, it refers to what remains in a 5 mm sieve by weight by 85% or more.

The water-soluble acrylic resin content of each of Examples was tested with a composition of 10% by weight, 20% by weight and 30% by weight based on the weight of cement. Here, the cement included in each of Comparative Examples to Examples is not limited to general cement, and may include super-fast-hardening cement and the like.

On the other hand, in the case of the component content and concrete test results of each of the comparative examples and examples in Table 2, and the average of the examples, the bending strength defined in the 2015 Korea Expressway Corporation standard specification is 3.15 MPa or more, the compressive strength is 21 MPa or more, and the adhesive strength is 1.4 MPa or more, slump value (mm) 10 ~ 60, and air amount (%) 5.5 ± 1.5 standards were all passed, and when compared with the average values of comparative examples, maximum flexural strength, maximum compressive strength, and maximum adhesive strength were respectively expressed.

That is, the concrete test results of the comparative examples and examples, when compared with the general specimen comparative example-no additives, the examples showed an effect of increasing the bending strength by up to 36% and increasing the bonding strength by up to 300%. This can be seen as the fact that the specific surface area of cement concrete is large, so the hydrogen bonding reaction surface of the polymer is widened and the strength is increased.

Preferably, in the scope of the embodiment, based on 100 parts by weight of the cement concrete mixture, 5 to 30 parts by weight of the water-soluble modified acrylic resin, 10 to 25 parts by weight of cement powder, 30 to 40 parts by weight of coarse aggregate and 30 to 45 parts by weight of fine aggregate are included. can

When the water-soluble modified acrylic polymer resin content is less than 5 parts by weight, the drying performance after mixing with other compositions may be greatly reduced and the adhesive strength may be reduced. In addition, if it exceeds 30 parts by weight, the degree of crosslinking may increase and cracking may occur, and the effect of developing compressive strength may be reduced due to the hydration reaction of concrete having a large proportion of unsaturated resin.

If the amount of cement powder is less than 10 parts by weight, the flexural strength and compressive strength may be lowered due to the insufficient amount of cement participating in the development of alkali-aggregate strength by the hydration reaction of cement concrete. Since it is impossible to secure pot life, the flowability of the mixture becomes excessively small, and workability may become very difficult.

If the amount of fine aggregate and coarse aggregate is less than 30 parts by weight, interlocking stress between aggregates may decrease, and if the amount of fine aggregate and coarse aggregate exceeds 45 parts by weight, the amount of air is relatively too large, and the effect of developing flexural strength and compressive strength is greatly reduced. It can be.

Therefore, the examples maintain the same level of compressive strength compared to general comparative example 1, conventional latex comparative example 2, and conventional modified epoxy comparative example 3, and have excellent flexural strength and adhesive strength development effect, thereby reducing the brittleness of cement concrete. It has the effect of expressing the ductility effect.

In addition, when the examples were compared with the conventional SB latex comparative examples, it was found that there was an equivalent level of average adhesion strength and compressive strength enhancement effect, which indicates that in the case of all examples, the solid content was around 20%, whereas the conventional SB latex In the case of the comparative example, when the latex solid content is 45% or more, considering the economic feasibility, it can be seen that the field applicability of the example is great.

The above embodiments are only exemplary, and various modifications and other equivalent embodiments may be made therefrom by those skilled in the art. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the invention described in the claims.

[Long-term fatigue test]

In order to verify the long-term fatigue performance of the inorganic cement mixture containing the one-component water-soluble modified epoxy-acrylic copolymer resin of the present invention, a comparative example and implementation of a half-neck load fatigue test using a 4-point flexural fatigue test apparatus as shown in FIG. It was conducted for example.

In FIG. 7, the results of the 4PB test under repeated loading at 30 ° C., in the case of the specimen of the comparative example, while the stiffness was high, cracks occurred in the member at 27,000 cycles, and the fatigue life was terminated. However, in the case of the example, the stiffness was kept small The fatigue life was extended without cracking for 53,000 cycles, which is about twice the number of loading times.

This shows that, as described above, other ductility is enhanced by the addition of the polymer resin, and the fatigue life can be greatly improved by dissipation or relief of stress caused by repeated loads applied to the member, while the stiffness is small.

In the case of the 4PB test results under repeated loading at 10 ° C. condition of FIG. 7, when the temperature is relatively low, the effect of extending the fatigue life is more evident.

As a result of the cyclic loading test under the condition of 10 ℃, the temperature is relatively low, and the stiffness is maintained high compared to the high temperature. In the case of the specimen of the comparative example, while the stiffness is high, cracks occur in the member at about 3,000 cycles, and the fatigue life In the case of the example, the initial stiffness was well maintained without cracking in the member for about 650,000 loading times.

Even in the case of the stress relaxation behavior of FIG. 8, in the case of the specimen of the comparative example, the internally generated stress is relatively large, and the initial stiffness is well maintained until the initial 1,000 cycles. , In the case of the example specimen, the initial stiffness is well maintained without cracking while the stress is relieved during 40,000 cyclic loads.

The first agent, the water-soluble modified epoxy resin, is prepared by mixing a bisphenol A or F-type epoxy resin, a carboxyl-terminated butadiene copolymer, a silane coupling agent, an unsaturated fatty acid, and ion-exchanged water;

The water-soluble modified acrylic resin as the second agent is prepared by mixing a styrene monomer, acrylonitrile, an emulsifier, and ion-exchanged water.

Referring to FIG. 9 , the components constituting the water-soluble modified epoxy resin as the first agent and the components constituting the water-soluble modified acrylic resin as the second agent are mixed in a stirrer 1.

In order to increase mixing efficiency of components in the agitator 1 and reduce generation of vibration and noise during the mixing process, the agitator 1 is installed on a mounting table 100.

The installation table 100 is provided with a shock dissipation means for absorbing the shock generated when the agitator 1 is driven and dispersing the applied shock to increase buffering efficiency.

Hereinafter, the mount 100 will be described with reference to FIGS. 10 to 12 . For reference, in the drawings, the components are slightly exaggerated (different from the actual dimensions) to easily understand the configuration and structure of the installation stand equipped with the impact dispersing means and the operating mechanism.

The mounting table 100 includes a bottom plate 110 placed on the floor, a buffer plate 120 disposed on the bottom plate 110 and on which the agitator 1 is placed, and the bottom plate 110 and the buffer plate 120. It includes a buffer spring 130 that is interposed in between and absorbs an impact applied on the buffer plate 120.

An impact generated during driving of the stirrer 1 installed on the buffer plate 120 is generally concentrated on a specific part. That is, the impact caused by the driving of the stirrer 1 is often concentrated on a specific part of the buffer plate 120 rather than being uniformly distributed throughout the buffer plate 120 . When the shock applied to the buffer plate 120 is concentrated on a specific part, the buffer plate 120 is tilted by the impact, and when the buffer plate 120 is tilted, the shock absorption efficiency is lowered, and the tilted buffer plate 120 is restored to its original position In the process of being tilted in the opposite direction, repeated shaking occurs, and the agitator 1 is pushed and moved on the inclined buffer plate 120, further reducing the shock absorption efficiency and making the inclination of the buffer plate 120 more severe .

In the present invention, even when an impact is applied to a specific part of the buffer plate 120, the shock absorber 120 is moved only in the vertical direction without tilting, so that the impact applied to the buffer plate 120 is reduced by introducing an impact dispersing means. While being uniformly distributed throughout the buffer plate 120, the above problems are solved.

The impact dispersing means includes a rotating plate 140 rotatably provided on the bottom plate 110, a plurality of first inclined blocks 150 provided on the rotating plate 140 and having an inclined surface 151 formed thereon, and , A plurality of second inclined blocks 160 having corresponding inclined surfaces 161 in contact with the inclined surface 151 formed at the lower part of the buffer plate 120 and formed on both sides of the first inclined block 150 It includes a slide rail 153 and a slide roller 163 provided on both sides of the second inclined block 160 and inserted into the slide rail 153 to move along the slide rail 153.

A bearing rotatably coupled to the rotating shaft 111 provided at the center of the bottom plate 110 is provided at the center of the lower surface of the rotating plate 140, and the rotating plate 140 is rotatably coupled to the upper surface of the bottom plate 110. ) It may be desirable to have a plurality of rotating balls or rotating rollers so that the rotation is made smoothly.

Guide holes 113 and guide pins 123 are provided at the corners of the bottom plate 110 and the buffer plate 120 to guide the lifting and lowering of the buffer plate 120, and the spring 130 passes through the rotating plate 140. A light through hole 141 having a round shape is formed.

When an impact is applied to a specific part of the buffer plate 120 and the part is pressed, the second inclined block 160 close to the impact part descends and the corresponding inclined surface 161 of the second inclined block 160 moves toward the first inclined block While moving along the inclined surface 151 of (150), the first inclined block 150 is pushed, and the rotating plate 140 rotates accordingly. When the rotary plate 140 rotates, the sliding rollers 163 provided on all the second inclined blocks 160 pull down their second inclined blocks 160 while moving along the restrained sliding rails 153. The buffer plate 120 is lowered.

As such, the shock dispersing means allows all of the second inclined blocks 160 to be simultaneously pulled down when an impact is applied to any part of the buffer plate 120, so that the buffer plate 120 moves downward without inclination. It is moved, and even when it is restored to its original position, it is moved upward without inclination.

In the above description of the present invention, softening cement concrete containing a water-soluble modified acrylic resin having a specific shape and structure has been described with reference to the accompanying drawings, but the present invention is capable of various modifications and changes by those skilled in the art, and such modifications and changes should be construed as falling within the protection scope of the present invention.

1: Agitator 100: Mounting stand
110: bottom plate 120: buffer plate
130: buffer spring 140: rotating plate
150: first company block 153: slide rail
160: second inclined block 163: sliding roller

Claims (4)

A composition in which a water-soluble modified epoxy resin as a first agent is added dropwise to a water-soluble modified acrylic resin as a second agent; and cement powder; and coarse aggregate; And fine aggregate; including,

The water-soluble modified epoxy resin as the first agent is
A bisphenol A or F type epoxy resin;
A carboxyl-terminated butadiene copolymer;
A silane coupling agent;
As a water-soluble resin in which unsaturated fatty acids are simultaneously entrained,
Based on 100 parts by weight of water-soluble modified epoxy resin
25 to 70 parts by weight of the bisphenol A-type or F-type epoxy resin;
1 to 5 parts by weight of the carboxyl-terminated butadiene copolymer;
1.0 to 2.5 parts by weight of the silane coupling agent;
20 to 60 parts by weight of the unsaturated fatty acids;
60 to 80 parts by weight of ion-exchanged water;

The water-soluble modified acrylic resin as the second agent is
with Stylen,
with acrylonitrile,
Characterized in that the emulsifier is a polymerized water-soluble resin
Soft cement concrete containing water-soluble modified acrylic resin. delete According to claim 1,
The water-soluble modified acrylic resin as the second agent is
Based on 100 parts by weight of water-soluble modified acrylic resin
10 to 30 parts by weight of the styrene;
1 to 10 parts by weight of the acrylonitrile;
The emulsifier is 0.5 to 5 parts by weight,
Characterized in that it comprises 60 to 80 parts by weight of ion-exchanged water
Soft cement concrete containing water-soluble modified acrylic resin. According to claim 1 or 3,
Components constituting the water-soluble modified epoxy resin as the first agent and components constituting the water-soluble modified acrylic resin as the second agent are mixed in a stirrer, and the stirrer is installed on a mounting table,
The mounting table has a bottom plate placed on the floor, a buffer plate disposed on the bottom plate and having the agitator placed thereon, a buffer spring interposed here and there between the bottom plate and the buffer plate to absorb shock applied to the buffer plate, and the buffer plate It includes an impact dispersing means for uniformly distributing the applied impact to the entire buffer plate,
The impact dispersing means includes a rotary plate rotatably provided on the bottom plate, a plurality of first inclined blocks provided on the rotary plate and having an inclined surface formed thereon, and a corresponding inclined surface provided on the buffer plate at a lower part contacting the inclined surface. A plurality of second slope blocks formed thereon, slide rails formed on both sides of the first slope block, and slide rollers provided on both sides of the second slope block and inserted into the slide rail to move along the slide rail characterized in that it contains
Soft cement concrete containing water-soluble modified acrylic resin.

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