KR20210017266A - Adhesive composition, use of the adhesive composition, method for preparing the adhesive composition, and method for applying the same - Google Patents

Abstract

The objective of the present invention is to provide an adhesive composition suitable for pouring concrete and mortar, which does not require overcoating of an upper coating agent in the pouring of concrete and mortar, exhibits excellent pouring performance (excellent strength) with respect to various bases such as dry, wetting, and lubricated bases, and has remarkably high generality compared to a conventional case. The adhesive composition comprises: an acrylic polymer which is formed from a monomer containing 1-30 wt% of an acrylic monomer having a tertiary amino group, wherein a glass transition temperature of the acrylic polymer is -20-50°C; an epoxy-based polymer; a neutralizing agent; an organic solvent; and water.

Description

Adhesive composition, use of adhesive composition, manufacturing method of adhesive composition, and construction method {ADHESIVE COMPOSITION, USE OF THE ADHESIVE COMPOSITION, METHOD FOR PREPARING THE ADHESIVE COMPOSITION, AND METHOD FOR APPLYING THE SAME}

The present invention relates to an adhesive used for construction purposes, in particular, an adhesive suitable for pouring new concrete or mortar onto an existing concrete or mortar base (hereinafter, simply referred to as "base material").

In general, in the case of pouring new concrete or mortar to the base, the surface of the base is roughened for the purpose of increasing the adhesion area and the seeding effect. This method can be expected to have some effect in the short term, but there is no adhesiveness to concrete and mortar in nature, leading to peeling someday. Therefore, conventionally, in order to prevent this peeling, a method of applying a primer composition to a base in advance and then pouring it has been proposed.

For example, Patent Document 1 discloses a primer formed by mixing an agent A containing an epoxy resin and a liquid chloroprene polymer as a main component, and an agent B containing a polyamide resin as a main component. In Patent Document 2, a primer containing an epoxy resin, a polyamine curing agent, a polysulfide polymer, and a tertiary amine compound is disclosed. Patent Document 3 discloses an adhesive composition for pouring comprising an epoxy resin, a water-dispersible polyamine epoxy adduct, a hydraulic cement, and a polyolefin resin-based pulp-like substance.

Further, in Patent Document 4, the use of an emulsion-based adhesive such as an acrylic styrene resin and an ethylene/vinyl acetate resin is disclosed. In Patent Document 5, a specific amount of a carboxyl group-containing polymerizable monomer (A), a specific amount of an alkoxysilane group-containing polymerizable monomer (B), a specific amount of an amide group-containing polymerizable monomer (C), and the above monomer (A) When any one or more of ~ (C) and a latex for a primer comprising a copolymer obtained by at least copolymerizing another polymerizable monomer (D) are described, and a mortar composition is adhered to the surface of a cement cured product, The purpose of using the latex is disclosed.

Further, in Patent Document 6, a bisphenol A-type liquid epoxy resin, a terminal aminated acrylonitrile-butadiene copolymer rubber, and a paint primer composition containing a solvent were applied to the adherend, and after drying the primer composition, epoxy Disclosed is a method of constructing a coating material, characterized in that applying a top coating material composed of a system composition.

Japanese Patent Laid-Open Publication No. 51-053538 Japanese Patent Laid-Open No. 2000-345101 Japanese Patent Laid-Open No. 2009-263424 Japanese Patent Laid-Open Publication No. 62-206169 Japanese Patent Publication No. 2015-098514 Japanese Patent Laid-Open Publication No. Hei 02-140276

In places such as metal processing factories that use large amounts of mineral oil or grease, or food factories that use large amounts of vegetable oil, the lower extremities are exposed to oils and fats over a long period of time, and the oils and fats may have penetrated to the very deep part of the lower extremities. Even if the surface of the base is cleaned by sand treatment or the like, it is not possible to completely remove the oils and fats that have penetrated the inside. The primer described in Patent Document 1 is proposed in order to apply to the lower limbs (hereinafter referred to as oily surfaces) into which oils and fats have penetrated.

On the other hand, in some cases, the lower limbs are exposed to water for a long period of time, and the water penetrates to the very deep part of the lower limb. Alternatively, in many cases, the deteriorated fragile layer and contamination on the surface of the base are washed and removed with high-pressure water before pouring. The primers described in Patent Documents 2 to 4 are proposed in order to be applied to a base (hereinafter referred to as a wet surface) to which water has penetrated.

There was a problem that the primer for oily surfaces described in Patent Document 1 cannot be applied to a wet surface. In addition, there is a problem that the primers for wetted surfaces described in Patent Documents 2 to 4 cannot be applied to the wetted surfaces.

In addition, the latex described in Patent Document 5 is proposed for the purpose of improving the adhesiveness in water and the adhesiveness at low temperatures after attaching the mortar composition to the surface of a cured cement product. However, there is a problem that the latex described in Patent Document 5 cannot be applied to the oily surface.

On the other hand, it is suggested that the primer described in Patent Document 6 is applicable to both a wet surface and an oily surface. However, the primer described in Patent Document 6 is used as a topcoat material and a set. In addition, it is necessary to apply a set of primers and topcoats each on both opposite sides of the adherend to be bonded, and the state after construction becomes adherend/primer/topcoat/topcoat/primer/adherent. That is, the primer described in Patent Literature 6 has a problem that it plays the role of the undercoat material in the upper coat material, and requires two types of ceramic materials for construction.

The present invention is compared with the prior art, which does not require overlapping of the top coat material in the pouring of concrete or mortar, and exhibits excellent pouring performance (excellent strength) for various dry, wet, or wet bases. It is an object of the present invention to provide an adhesive composition suitable for subsequent pouring of concrete or mortar with remarkably high versatility.

One embodiment of the present invention has been made in view of the above problems, and relates to an adhesive composition containing a specific acrylic polymer and an epoxy polymer, and further use of the adhesive composition for swelling, an adhesive composition It relates to a method of manufacturing, and a construction method.

(1) Acrylic polymer, epoxy polymer, neutralizing agent, organic solvent, and water, formed from a monomer containing 1 to 30% by mass of an acrylic monomer having a tertiary amino group, and having a glass transition temperature of -20 to 50°C. Containing, used for pouring concrete or mortar, the adhesive composition.

(2) The above-mentioned (1), wherein the monomer further contains at least one selected from the group consisting of a (meth)acrylic monomer having no hydroxyl group, a monomer having an aromatic ring, and a monomer having a hydroxyl group. Adhesive composition.

(3) The adhesive composition according to (1) or (2), comprising 5 to 50 parts by mass of the epoxy polymer with respect to 100 parts by mass of the acrylic polymer.

(4) The adhesive composition according to any one of (1) to (3), comprising 10 to 60 mass% of the organic solvent and the water in total.

(5) The adhesive composition according to any one of (1) to (4), wherein the ratio of the organic solvent to the water is organic solvent: water = 30 to 90: 10 to 70 (mass ratio).

(6) As the use of an adhesive composition used for pouring concrete or mortar, the adhesive composition is formed from a monomer containing 1 to 30% by mass of an acrylic monomer having a tertiary amino group, and the glass transition temperature is- Use containing acrylic polymers, epoxy polymers, neutralizing agents, organic solvents, and water at 20 to 50°C.

(7) The above-mentioned (6), wherein the monomer further contains at least one selected from the group consisting of a (meth)acrylic monomer having no hydroxyl group, a monomer having an aromatic ring, and a monomer having a hydroxyl group. use

(8) The use according to (6) or (7), wherein the adhesive composition contains 5 to 50 parts by mass of the epoxy polymer with respect to 100 parts by mass of the acrylic polymer.

(9) The use according to any one of (6) to (8), wherein the adhesive composition contains 10 to 60 mass% in total of the organic solvent and the water.

(10) The use according to any one of (6) to (9), wherein the ratio of the organic solvent to the water is organic solvent: water = 30 to 90: 10 to 70 (mass ratio).

(11) As a method for producing the adhesive composition according to any one of (1) to (5) above, or the adhesive composition used for use according to any of (6) to (10) above, a tertiary amino group A step of preparing an acrylic polymer solution by mixing an acrylic polymer having a glass transition temperature of -20 to 50°C, a neutralizing agent, and an organic solvent, formed from a monomer containing 1 to 30% by mass of an acrylic monomer, and an epoxy polymer And an epoxy-based polymer solution containing an organic solvent, the acrylic polymer solution, and water.

(12) A construction method in which concrete or mortar is poured together after applying the adhesive composition according to any one of (1) to (5) to the base.

(13) A construction method in which a mixture obtained by mixing the adhesive composition according to any one of the above (1) to (5) to concrete or mortar is poured into the base.

According to the embodiment of the present invention, excellent puffing performance (excellent strength) can be exhibited with respect to various dry, wet, or oily bases, so that it is not necessary to overwrite the adhesive to the base. In addition, since there is no need to overlap the topcoat, construction becomes simple and work efficiency is improved.

As described above, the adhesive composition of the embodiment of the present invention contains acrylic polymer, epoxy polymer, neutralizing agent, organic solvent, and water, and exhibits excellent spouting performance for concrete in various states. can do.

<Acrylic polymer>

The acrylic polymer in the embodiment of the present invention is formed by polymerizing a monomer essential to an acrylic monomer having a tertiary amino group. As an acrylic monomer having a tertiary amino group, an acrylic monomer having a dialkylamino group can be mentioned, for example. The acrylic polymer is preferably used in the form of an acrylic polymer solution containing a neutralizing agent and an organic solvent, mixed with an epoxy polymer solution described later.

A monomer referred to in this specification and the like refers to a compound having an ethylenically unsaturated double bond capable of radical polymerization. In addition, an acrylic monomer is an abbreviation of the monomer which has an acryloyl group and/or a methacryloyl group. Accordingly, the monomers referred to in the present specification and the like include acrylic monomers having no tertiary amino group, acrylic monomers other than acrylic monomers, etc. in addition to the acrylic monomer having a tertiary amino group.

Examples of acrylic monomers that do not have a tertiary amino group and monomers other than acrylic monomers include (meth)acrylate monomers that do not have functional groups such as hydroxyl groups, those that have an aromatic ring, those that have a hydroxyl group, and that which have a carboxyl group. What has a thing, what has an amide group, what has an epoxy group, what has an alicyclic structure, (meth)acrylate alkoxyester, a vinyl ester, etc. are mentioned. It is preferable to use two or more types of monomers.

On the other hand, (meth)acrylate is the meaning of acrylate and/or methacrylate, and (meth)acrylic acid is the meaning of acrylic acid and/or methacrylic acid.

As the acrylic monomer having a tertiary amino group, a known compound can be used. For example, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, and (meth)acrylate ) (Meth)acrylate dialkylamino esters such as diisopropylaminoethyl acrylate and dibutylaminoethyl (meth)acrylate. In the embodiment of the present invention, as described later, it is mixed with an epoxy polymer solution and has a tertiary amino group in 100% by mass of the monomer from the balance of the compatibility when diluted with water and the adhesion strength on the wet and oily surfaces. It is important to contain 1-30 mass% of acrylic monomers, and it is preferable to contain 5-20 mass %.

As the (meth)acrylic monomer that does not have a functional group such as a hydroxyl group, known compounds can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl ( Meth)acrylate, and n-tetradecyl (meth)acrylate.

As the monomer having an aromatic ring, a known compound can be used, for example, phenyl acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, biphenyl (meth) acrylate, styrene, Vinyl toluene, and α-methylstyrene.

As a monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl ( Meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, acrylic acid (4-hydroxymethylcyclohexyl)methyl , N-methylol (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether.

As the monomer having a carboxyl group, a known compound can be used, for example, (meth)acrylic acid, (meth)acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid , Itaconic acid, acrylamide N-glycolic acid, and cinnamic acid.

As the monomer having an amide group, a known compound can be used. For example, (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-di Ethyl (meth)acrylamide, N,N'-methylenebisacrylamide, N-methylol (meth)acrylamide, N-ethylol (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N- Vinylpyrrolidone, diacetone acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and (meth)acryloylmorpholine, and the like.

As the monomer having an epoxy group, a known compound can be used, and examples thereof include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and allyl glycidyl ether.

As a monomer having an alicyclic structure, known compounds can be used, and examples thereof include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate.

As the (meth)acrylate alkoxy ester, a known compound can be used, for example, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate , 3-methoxypropyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, and the like.

As the vinyl ester, a known compound can be used, and examples thereof include vinyl acetate, vinyl propionate, and vinyl laurate.

In addition, in the embodiment of the present invention, it is important to select the type and amount of the monomer so that the glass transition temperature (Tg) of the acrylic polymer is -20 to 50°C from the viewpoint of maintaining adhesive strength. It is more preferable to select to be. On the other hand, in the embodiment of the present invention, the glass transition temperature (Tg) of the acrylic polymer can be determined by a differential scanning calorimeter (DSC) as described later.

The acrylic polymer can be produced by polymerizing a monomer in an organic solvent using a polymerization initiator. In polymerization, a compound having a chain transfer effect may be used to control molecular weight.

Examples of the organic solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, esters, alcohols, and ketones.

As an aliphatic hydrocarbon, well-known compounds, such as n-hexane and n-heptane, are mentioned, for example.

Alicyclic hydrocarbons are, for example, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydro Known compounds, such as indencyclohexane, cyclooctane, α-pinene, terpinolene, and limonene, can be mentioned.

As an aromatic hydrocarbon, known compounds, such as toluene, xylene, benzene, and solvent naphtha, are mentioned, for example.

Examples of the ester include known compounds such as ethyl acetate and butyl acetate.

Examples of the alcohol include known compounds such as n-propyl alcohol and isopropyl alcohol.

As the ketone, known compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example. Ketones also have a function of chain transfer.

In the embodiment of the present invention, the organic solvent can be used alone or in combination of two or more among the above, and the organic solvent can be selected in consideration of the coatability of the adhesive composition.

Examples of the radical polymerization initiator used when producing the acrylic polymer include an azo compound and a peroxide. Moreover, radical polymerization initiators can be used alone or in combination of two or more.

Examples of the azo compound include 2,2'-azobis(2-methylbutyronitrile), and 2,2'-azobisisobutyronitrile.

Peroxides are t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, di-t-butyl peroxide, and 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclo Hexane, etc. are mentioned.

As a compound having a chain transfer effect, in addition to the above-described ketone-based organic solvent, thiol, tackifying resin, and the like can be mentioned. Compounds having a chain transfer effect can be used alone or in combination of two or more.

Thiols are, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiosaconic acid, 2-mercaptoethanesulfonic acid, butanethiol, octanethiol, decanethiol, docanthiol, hexadecanethiol , Octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, and octyl 3-mercaptopropionate.

Tackifying resins are, for example, rosin-based resins, polymerized rosin-based resins, rosin ester-based resins, polymerized rosin-ester-based resins, terpene-based resins, terpenephenol-based resins, coumarone-based resins, coumarone-indene-based resins, and styrene-based Known resins, such as resin, xylene resin, phenol resin, and petroleum resin, are mentioned.

Examples of the neutralizing agent used to neutralize the tertiary amino group in the acrylic polymer include inorganic acids such as hydrochloric acid, sulfuric acid, sulfamic acid, and nitric acid, organic acids such as phosphoric acid, formic acid, acetic acid, propionic acid, and oxalic acid, ethyl bromide, butyl bromide, and benzyl bromide. , Alkyl halides such as methyl chloride, ethyl chloride, benzyl chloride, and methyl iodide, or inorganic acid esters such as aralkyl halides, dimethyl sulfate, and diethyl sulfate, and epihalides such as epichlorohydrin and epibromhydrin Rohydrin, etc. are mentioned. It is preferable to use an organic acid such as formic acid or acetic acid.

The amount of the neutralizing agent is preferably 50 to 300% in terms of the number of functional groups with respect to the tertiary amino group, from the viewpoint of the ease of dilution of the adhesive composition with water, the viscosity, and the reactivity of the acrylic polymer and the epoxy polymer. % Is more preferred.

<epoxy clock polymer>

The epoxy polymer used in the embodiment of the present invention is not particularly limited as long as it is a liquid or solid resin having two or more epoxy groups per molecule on average, and may further be a mixture of these. The epoxy-based polymer is preferably used in a state of an epoxy-based polymer solution containing an epoxy-based polymer and an organic solvent, mixed with the above-described acrylic polymer solution.

Examples of the epoxy polymer include polyglycidyl ether obtained by reacting a polyhydric alcohol such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol with epichlorhydrin; Glycidyl ether ester obtained by reacting a hydroxylcarboxylic acid such as P-hydroxybenzoic acid with epichlorhydrin; Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorhydrin; In addition, phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, epoxidized polyolefins, alicyclic epoxy resins, and urethane-modified epoxy resins may be mentioned, but are not limited thereto.

As the organic solvent used in the epoxy-based polymer solution, those exemplified in the case of the acrylic polymer can be used.

<Adhesive composition>

The adhesive composition of the embodiment of the present invention can be produced by mixing the above-described acrylic polymer solution and epoxy polymer solution, and diluting with water. By diluting with water, it is possible to firmly attach new concrete or the like to the wet surface. The adhesive composition according to the embodiment of the present invention preferably contains 5 to 50 parts by mass, and more preferably 15 to 25 parts by mass, of an epoxy polymer per 100 parts by mass of the acrylic polymer.

The content of the organic solvent and water is not limited, but when the non-volatile content is adjusted to 30% by mass, it is preferable to adjust the amount so that the viscosity at 25°C of the adhesive composition becomes 100 to 2000 mPa·s, and 200 It is more preferable to adjust the amount so that it may be -800 mPa·s. In order to make the adhesive composition of such viscosity, for example, it is preferable to contain 10 to 60 mass% of organic solvent and water in total, and the ratio of organic solvent and water is organic solvent: water = 30 to 90: 10 to 70 It is preferable that it is (mass ratio).

The adhesive composition satisfying such a non-volatile content and viscosity improves the coatability. On the other hand, the viscosity is the viscosity measured after 60 minutes after mixing the acrylic polymer solution, the epoxy polymer solution, and water, using a BL-type viscometer in an atmosphere of 25°C, 1 minute after the start of rotation with a #3 rotor and a rotation speed of 12 rpm. to be.

The adhesive composition of the embodiment of the present invention is additionally an optional component as a flame retardant, a heat stabilizer, a weather stabilizer, an anti-aging agent, an ultraviolet absorber, a leveling agent, an antistatic agent, a slip agent, an anti-blocking agent, an antifogging agent, a lubricant, a dye. , Wax, emulsion, magnetic material, or a dielectric property modifier.

The bonding composition according to the embodiment of the present invention can be used when applying to an existing concrete or an existing mortar and pouring a new concrete or a new mortar together. As a coating method of the adhesive composition, a known coating method such as brush, trowel, roll, or spray can be used. The thickness of the adhesive composition is preferably about 10 to 200 μm in consideration of the balance between cost and adhesive performance.

Furthermore, it is also possible to pour concrete or the like containing the bonding composition in which the bonding composition of the embodiment of the present invention is mixed in new concrete or in a new mortar, to an existing concrete or an existing mortar. The pouring can be used for various purposes, such as pillars, walls, and floors of buildings, outdoor pavements, sites, tunnels, and bridges.

Example

Hereinafter, specific examples of the embodiments of the present invention will be described together with comparative examples, but the embodiments of the present invention are not limited to the following examples. In addition, in the following Examples and Comparative Examples, "part" and "%" represent "part by mass" and "% by mass", respectively.

The monomers, polymerization initiators, and organic solvents used in this example are listed below.

<Monomer>

DM: Dimethylaminoethyl (meth)acrylate

DE: diethylaminoethyl (meth)acrylate

St: styrene

2EHA: 2-ethylhexylacrylate

2HEA: 2-hydroxyethyl acrylate

<Polymerization initiator>

AIBN: Azobisisobutyronitrile

<Organic solvent>

EC: ethyl cellosolve

BC: Butyl Cellosolve

IPA: isopropyl alcohol

<Measurement of non-volatile content>

About 1 g of the sample solution was weighed in a metal container, dried in an oven at 150° C. for 20 minutes, and the residue was weighed and the residual ratio was calculated to obtain a non-volatile content (non-volatile content concentration).

<Measurement of molecular weight (Mw)>

The mass average molecular weight (Mw) was measured by gel permeation chromatography (GPC). As a measuring device, Tosoh Corporation GPC "HPC-8020" was used. As a column, a product obtained by connecting two SuperHM-M and SuperHM-L manufactured by Tosoh Corporation in series was used. It measured at 40 degreeC using tetrahydrofuran (THF) as a solvent (eluent). On the other hand, the mass average molecular weight (Mw) was all converted into polystyrene as a standard.

<Measurement of glass transition temperature (Tg)>

The glass transition temperature (Tg) was determined by measurement with a differential scanning calorimeter (DSC). "SSC5200 Disk Station" (manufactured by Seiko Instruments) was connected to a robot DSC (differential scanning calorimeter, "RDC220" manufactured by Seiko Instruments Inc.), and used for measurement.

The solution of the acrylic polymer prepared in each Synthesis Example was coated and dried on a polyester peelable film substrate, and the dried product was used as a measurement sample. 10 mg of a sample for measurement was set in the differential scanning calorimeter, maintained at 100°C for 5 minutes, and then rapidly cooled to -120°C using liquid nitrogen. Then, the temperature was raised at a temperature increase rate of 10°C/min, the temperature was raised to 200°C, and DSC measurement was performed. The glass transition temperature (Tg) (unit: °C) was determined from the obtained DSC chart.

[Synthesis Example 1]

St: 48 parts, 2EHA: 22 parts, 2HEA: 20 parts, and DM: 10 parts, BC: 50 parts, polymerization using AIBN, mass average molecular weight (Mw): 15000, further glass transition temperature: 20 C. acrylic polymer was prepared, BC: 15 parts, EC: 40 parts, IPA: 40 parts, and acetic acid: 5 parts were added as a neutralizing agent, and non-volatile content: 40% acrylic polymer solution [A1] was added. Was produced. The acrylic polymer solution [A1] contains BC: 65 parts, EC: 40 parts, IPA: 40 parts, and acetic acid: 5 parts with respect to about 100 parts of the acrylic polymer.

[Synthesis Examples 2 to 9, 13 to 16]

In the same manner as in Synthesis Example 1, except that the monomer species and its amount, the kind and amount of the neutralizing agent, and the amount of the organic solvent were changed as shown in Table 1, the mass average molecular weight (Mw) was 15000, and Solutions [A2] to [A9], and [A13] to [A16] containing an acrylic polymer having a transition temperature of -25 to 55°C and having a nonvolatile content of 40% were prepared.

[Synthesis Examples 10 to 11]

Except having changed the amount of AIBN, in the same manner as in Synthesis Example 1, non-volatile content: 40% acrylic polymer solutions [A10] and [A11] having a mass average molecular weight (Mw) of 30000 and 7500 were prepared.

[Synthesis Example 12]

In the same manner as in Synthesis Example 1, except for using BC: 30 parts as a solvent during polymerization, EC: 40 parts, IPA: 40 parts, water: 35 parts as a diluent, mass average molecular weight (Mw): 15000, and, Glass transition temperature: A solution [A12] containing an acrylic polymer at 20°C and having a nonvolatile content of 40% was prepared.

On the other hand, the acrylic polymer solution [A12] and the acrylic polymer solution [A1] differ in the solvent composition in which the acrylic polymer having the same component, glass transition temperature, and mass average molecular weight is dissolved.

[Example 1]

With respect to 100 parts of the acrylic polymer solution described in Synthesis Example 1 (including about 40 parts of the acrylic polymer), as the epoxy polymer solution [B1], a bisphenol A liquid epoxy polymer (JER828 manufactured by Mitsubishi Chemical Co., Ltd. epoxy equivalent 184 to 194 ) 20 parts of an ethyl cellosolve solution of about 70% of non-volatile content (including about 14 parts of the epoxy-based polymer), and 60 parts of water as a diluent were added, and sufficiently stirred, to prepare an adhesive composition. The nonvolatile content of this adhesive composition was 30%.

According to the method described later, the strength of pouring concrete on the dry, wet, and oily surfaces was evaluated.

[Examples 2 to 11]

As shown in Table 2, an adhesive composition having a nonvolatile content of 30% was prepared in the same manner as in Example 1 except that the acrylic polymer solution was changed, and the same evaluation was performed.

[Examples 12-14]

As shown in Table 2, an adhesive composition having a nonvolatile content of 30% was obtained in the same manner as in Example 1, except that the diluent was changed, and evaluated in the same manner.

[Examples 15 to 16]

As an epoxy polymer solution, in place of the above [B1], in Example 15, as an epoxy polymer solution [B2], the nonvolatile content of the bisphenol A-type solid epoxy polymer (JER1002 epoxy equivalent 600-700 manufactured by Mitsubishi Chemical Co., Ltd.) % Ethyl cellosolve solution), in Example 16, a phenol novolak-type liquid epoxy polymer (JER154 Mitsubishi Chemical Co., Ltd. epoxy equivalent of 176 to 180), an ethyl cellosolve solution of about 70% of nonvolatile content) , Except having used each, it carried out similarly to Example 1, and produced the adhesive composition with a non-volatile content of 30%, and evaluated similarly.

[Examples 17 to 18]

As shown in Table 2, an adhesive composition having a nonvolatile content of 30% was prepared in the same manner as in Example 1, except that the amount of the epoxy polymer solution [B1] to be mixed and the amount of the diluent were changed, and evaluated in the same manner. .

[Comparative Examples 1-5]

As shown in Table 2, an adhesive composition having a nonvolatile content of 30% was prepared in the same manner as in Example 1 except that the acrylic polymer solution and the diluent were changed, and the same evaluation was performed.

[Comparative Example 6]

Bisphenol A liquid epoxy polymer (JER828, manufactured by Mitsubishi Chemical Co., Ltd.): 100 parts, chloroprene rubber: 90 parts, nonylphenol 10 parts, xylene resin: 20 parts, and methyl isobutyl ketone 20 parts are mixed to form the first The solution was prepared. In addition, polyamide amine resin (Lucamide TD-984, manufactured by DIC Corporation): 120 parts, 2,4,6-tris(dimethylaminomethyl)phenol 5 parts, zinc oxide 5 parts, heavy calcium carbonate powder 50 A second solution was prepared by mixing 20 parts of parts, xylene resin (Nikanol Y-100, manufactured by Fudo Corporation), 25 parts of dioctylphthalate, and 25 parts of toluene. The first liquid and the second liquid were mixed to prepare an adhesive composition, and evaluated in the same manner as in Examples.

[Comparative Example 7]

Bisphenol A type liquid epoxy polymer (JER828 manufactured by Mitsubishi Chemical Corporation): 100 parts, modified aliphatic polyamine resin (manufactured by Luckamide WH-614 Corporation): 6 parts, liquid polysulfide (Thiocol LP-3 Toray (Co., Ltd.): 10 parts and 2,4,6-tris(dimethylaminomethyl)phenol: 1 part were mixed to prepare an adhesive composition, and evaluated in the same manner as in Examples.

[Comparative Example 8]

Methyl methacrylate (MMA): 396 parts by mass, 2-ethylhexyl acrylate (2-EHA): 577 parts by mass, methacrylic acid (MAA): 20 parts by mass, acrylamide (AAm): 2 parts by mass, and γ -Methacryloxypropyltrimethoxysilane: 5 parts by mass, in the presence of a nonionic emulsifier, was subjected to emulsion polymerization using ammonium peroxodisulfate, and then the pH was adjusted to 8 with aqueous ammonia, and the nonvolatile content was about 46%. A composition for phosphorus bonding was prepared and evaluated in the same manner as in Examples.

[Strength evaluation]

The surface of 300 mm × 300 mm of a 300 mm × 300 mm × 60 mm concrete plate was subjected to sand treatment to remove the weak part of the surface, and a dry concrete base was obtained.

<Dry noodles>

The dry concrete base was coated with a brush so that the adhesive composition was 150 g/m ² in a solution state. After drying for 1 hour in an atmosphere of 20°C, the mortar was applied to a thickness of 10 mm using an iron trowel, and the sample subjected to pouring was cured for 28 days in an atmosphere of 20°C. A 40 mm steel jig was bonded with an epoxy-based bonding composition, and after curing the bonding composition, a sheath reaching the concrete plate was placed around the steel jig with a diamond cutter, and the adhesion was measured with a dry-roll adhesion tester. Evaluate as.

A: The whole surface becomes concrete or mortar fracture, and it is good without interfacial peeling and cohesive failure of the adhesive composition between concrete and mortar.

B: The practical lower limit of the exposure of the interface between the concrete and the adhesive composition is less than 5%

C: Not practical because the exposure of the interface between the concrete and the adhesive composition is 5% or more, or the cohesive failure of the adhesive composition layer

<wet cotton>

The dry concrete base was immersed in water for 48 hours, the surface was wiped with waste, and then the adhesive composition was applied as in the case of <dry surface>, and then mortar was applied and evaluated.

<Yooyunmyeon>

The dry concrete base was immersed in oil (vegetable oil: animal oil = 1:1 (mass ratio) for 48 hours, and the surface was wiped with a waste, and then the adhesive composition was applied as in the case of <dry surface>, Mortar was applied and evaluated.

From Table 2, it can be seen that the adhesive composition of this example exhibits excellent adhesive performance on the dry, wet, and oily surfaces.

On the other hand, in the adhesive composition of Comparative Example 1, when there are few acrylic monomers having a tertiary amino group (0.5% by mass), the compatibility with water decreases, resulting in poor adhesion on the wet surface, and the adhesion of Comparative Example 2 It can be seen that when the solvent composition contains a large number of acrylic monomers having a tertiary amino group (40% by mass), the compatibility with oil decreases, resulting in poor adhesion on the oily surface. In addition, when the glass transition temperature of the acrylic polymer is low (Tg: -25°C), the adhesive composition of Comparative Example 3 has a low elasticity as an adhesive composition, so it adheres to any of the dry, wet, and oily surfaces. Performance is inferior, and the adhesive composition of Comparative Example 4 has a low viscosity of the adhesive composition when the glass transition temperature of the acrylic polymer is high (Tg: 55°C), and therefore, in any of the dry, wet, and oily surfaces It can be seen that the adhesion performance is inferior. Further, in the adhesive composition of Comparative Example 5, since the adhesive composition does not contain water, the wettability of the adhesive composition to the wet surface is low, and the impermeability to concrete is poor, so the adhesiveness is inferior, and Comparative Example 6 Since the adhesive composition of the composition contains a resin having low affinity with water, the wettability of the adhesive composition to the wet surface is low, and the impregnation to concrete is poor, so the adhesiveness is inferior, and the adhesive composition of Comparative Example 7 Since the affinity with silver and water was increased, the correspondence with oil was low and the adhesion on the oily surface was poor.The adhesive composition of Comparative Example 8 has low affinity with oil, so the wettability to the oily surface It can be seen that this is low and the adhesion to concrete is poor, so the adhesion is inferior.

The bonding composition of the embodiment of the present invention can be used not only for pouring concrete or mortar, but also as a primer for repairing floors, roofs, verandas, and exterior walls.

Claims (13)

It is formed from a monomer containing 1 to 30% by mass of an acrylic monomer having a tertiary amino group, and contains an acrylic polymer having a glass transition temperature of -20 to 50°C, an epoxy polymer, a neutralizing agent, an organic solvent, and water. , Used for pouring concrete or mortar, the adhesive composition. The method of claim 1,
The above-mentioned monomer further comprises at least one selected from the group consisting of a (meth)acrylic monomer having no hydroxyl group, a monomer having an aromatic ring, and a monomer having a hydroxyl group. The method according to claim 1 or 2,
An adhesive composition comprising 5 to 50 parts by mass of the epoxy polymer based on 100 parts by mass of the acrylic polymer. The method according to claim 1 or 2,
An adhesive composition comprising 10 to 60% by mass of the organic solvent and the water in total. The method according to claim 1 or 2,
The ratio of the organic solvent to the water, organic solvent: water = 30 ~ 90: 10 ~ 70 (mass ratio), the adhesive composition. As the use of an adhesive composition used for pouring concrete or mortar,
The adhesive composition is formed from a monomer containing 1 to 30% by mass of an acrylic monomer having a tertiary amino group, an acrylic polymer having a glass transition temperature of -20 to 50°C, an epoxy polymer, a neutralizing agent, and an organic solvent. Wow, use containing water. The method of claim 6,
The use of the monomer further comprises at least one selected from the group consisting of a (meth)acrylic monomer having no hydroxyl group, a monomer having an aromatic ring, and a monomer having a hydroxyl group. The method according to claim 6 or 7,
The use of the adhesive composition, containing 5 to 50 parts by mass of the epoxy polymer based on 100 parts by mass of the acrylic polymer. The method according to claim 6 or 7,
The adhesive composition contains 10 to 60 mass% of the organic solvent and the water in total. The method according to claim 6 or 7,
Use, wherein the ratio of the organic solvent and the water is organic solvent: water = 30 to 90: 10 to 70 (mass ratio). A method for producing an adhesive composition according to claim 1 or 2, or an adhesive composition used for use according to claim 6 or 7,
A step of preparing an acrylic polymer solution by mixing an acrylic polymer formed from a monomer containing 1 to 30% by mass of an acrylic monomer having a tertiary amino group and having a glass transition temperature of -20 to 50°C, a neutralizing agent, and an organic solvent. ,
A method for producing an adhesive composition comprising a step of mixing an epoxy-based polymer solution containing an epoxy-based polymer and an organic solvent, the acrylic polymer solution, and water. A construction method in which concrete or mortar is poured together after applying the adhesive composition according to claim 1 or 2 to a base. A construction method in which a mixture obtained by mixing the adhesive composition according to claim 1 or 2 with concrete or mortar is poured into the base.