JPH1129348A - Concrete forming composition - Google Patents

Abstract

(57) [Problem] To provide a concrete forming composition for forming concrete having excellent acid resistance and corrosion resistance and non-adhesiveness. SOLUTION: The composition for concrete formation containing a fluororesin emulsion, wherein the minimum film forming temperature of the fluororesin emulsion is lower than the temperature at the time of concrete hardening.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concrete forming composition for forming concrete having excellent durability and non-adhesiveness, and a concrete using the same.

[0002]

2. Description of the Related Art Concrete is considered to have high durability and fire resistance and is relatively inexpensive. Therefore, concrete has been widely used as a building, an outdoor building, a bridge and the like for more than 100 years. The concrete-forming composition for forming concrete comprises about 9 to 15% by volume of cement,
It is composed of about volume% of water, other aggregates and the like, and after containing necessary admixtures, is poured into molds having various shapes and waits for hardening with time to become concrete.

[0003] Cement, which is a main component of a concrete forming composition, hardens by a chemical reaction with water to form a main part of concrete. Aggregate is blended for the purpose of preventing a decrease in strength due to shrinkage when concrete is formed only with cement. The admixture is used for the purpose of reducing the amount of water to improve the durability of concrete, reducing the heat of hydration, preventing cracks, improving long-term strength, and suppressing abnormal expansion of aggregate. To be contained.

When such concrete is used for a long period of time, the concrete itself is oxidized and deteriorates, and furthermore, eroded by microorganisms and deteriorated.
In particular, when used in a place where it comes into contact with strong acid water such as hot spring water, it is strongly oxidized. In addition, when used as a water treatment facility such as a revetment block, a cooling introduction channel, an aquaculture tank, or a water tank, erosion by microorganisms is severe.

In order to prevent such erosion, a method for suppressing the generation of sulfide in sewage, which directly causes deterioration of a concrete structure, a method for oxidizing or solidifying the sulfide, and a method for preventing corrosion are provided. Methods such as painting or lining concrete have been adopted, but have not yet reached an essential solution.

Japanese Patent Application Laid-Open No. Hei 9-12380 discloses that a fluororesin and copper / titanium /
An agent for preventing deterioration of a concrete structure in which a cement containing nickel powder is dispersed in water is disclosed. However, since the copper / titanium / nickel powder used here is a simple antibacterial agent, it has only an effect of preventing the propagation of microorganisms, and has a drawback that the effect gradually decreases.

When such concrete is used for pavement on a sidewalk of a road, a platform of a station, a playground of a park, or the like, pedestrians and schoolchildren exhale an adhesive substance such as gum, which solidifies and becomes aesthetically pleasing. However, there is no way to solve these problems with conventional concrete.

[0008]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a concrete forming composition for forming concrete having excellent acid resistance and corrosion resistance and having no tackiness. It is assumed that.

[0009]

The concrete-forming composition of the present invention contains a fluororesin emulsion, and the minimum film-forming temperature of the fluororesin emulsion is lower than the temperature at the time of concrete hardening. It is assumed that. Hereinafter, the present invention will be described in detail.

[0010] The concrete forming composition of the present invention comprises a cement, which is contained in a usual concrete forming composition,
Water, aggregate, and admixtures contain other additives. The above-mentioned cement, aggregate, and admixture are not particularly limited, and include conventionally known ones.

[0011] The water is not particularly limited, and water generally used for concrete can be used, for example, tap water. The amount of the water can be appropriately selected depending on the purpose of the concrete and the like.
(Weight of cement)] is preferably 40 to 70%.

As the cement, limestone (CaO)
And clay, silica stone, iron oxide, etc. (SiO ₂ , Al ₂ O ₃ ,
Fe ₂ O ₃ ) is fired at a high temperature of about 1450 ° C. to obtain clinker, to which a setting modifier (eg, gypsum) such as calcium sulfate is added and finely pulverized. And the like, and for example, commercially available Portland cement can be used. Examples of the Portland cement include, for example, early-strength Portland cement, ultra-high-strength Portland cement, moderately heated Portland cement, sulfate-resistant Portland cement, white Portland cement, and the like, depending on the application. Also, mixed cements other than Portland cement and special cements can be used in the composition for concrete formation of the present invention.

The amount of the cement can be appropriately selected according to the application of the concrete to be formed, but is usually preferably 5 to 20% by volume based on the whole concrete forming composition containing water.

The above-mentioned aggregate is not particularly limited. Examples of the natural aggregate include river gravel, river sand, land gravel, land sand, mountain sand, sea sand, and the like. Crushed stones and crushed sand; volcanic sand created by volcanic eruptions;
Silica sand and the like can be mentioned. The artificial aggregate is, for example, an artificial lightweight aggregate made by firing fly ash, which is a fine combustion ash of shale and coal; a molten slag produced when iron is separated in a blast furnace; Blast furnace slag aggregate and the like. These may be used alone or in combination of two or more.

The amount of the above-mentioned aggregate can be appropriately selected according to the use of the concrete to be formed.
0% by volume.

The admixture used in the concrete forming composition of the present invention is not particularly limited, and examples thereof include fly ash, blast furnace slag fine powder, silica fume and the like. One or more of these can be selected and used as needed. In addition to the admixtures described above, the concrete-forming composition of the present invention includes an AE agent that generates fine and independent air bubbles in concrete, a water reducing agent used to reduce the amount of water required, and a coagulation agent. Accelerators for shortening the time, quick setting agents, retarders for increasing the setting time, and the like can be blended as required.

The concrete forming composition of the present invention contains a fluororesin emulsion. The minimum film forming temperature of the fluororesin emulsion is lower than the temperature at the time of concrete hardening.

In the present specification, the temperature at the time of concrete hardening means the temperature at which the concrete forming composition of the present invention hardens. The concrete hardening temperature is affected by heat (hydration heat) generated by a chemical reaction between water and cement, and is also affected by an external temperature such as a season. , 33
３８38 ° C.

In the present specification, the minimum film forming temperature is J
It is the minimum film-forming temperature defined in IS K 6828, and means the temperature at which water evaporates from the emulsion and the particles fuse with each other to form a continuous film. The minimum film formation temperature (MFT) is measured by a mechanical method of measuring using a temperature gradient hot plate type minimum film formation temperature measuring instrument, and assuming a temperature range suitable for a sample to be measured, the minimum film formation temperature is measured. Set the temperature on the high temperature side and the low temperature side so that the temperature difference between the minimum and maximum can be measured in the range of 20 to 40 ° C. It is determined by the method of quickly applying to the side, reading the lowest temperature at which a continuous and uniform film without cracks is formed, and setting the lowest film forming temperature. In the present specification, the minimum film forming temperature of the fluororesin emulsion is
It means the minimum film forming temperature of the fluororesin itself, or the minimum film forming temperature of the entire fluororesin emulsion when a film forming aid is added to the fluororesin.

If the minimum film forming temperature of the fluororesin emulsion used in the present invention is higher than the temperature at the time of concrete hardening, the fluororesin emulsion in the composition for concrete formation cannot be formed into a satisfactory film. The specific effects of the invention cannot be achieved. The present inventors have reached the present invention for the first time by discovering this fact.

Hereinafter, the fluororesin emulsion contained in the concrete forming composition of the present invention will be described in detail. The fluororesin emulsion can be roughly classified into the following six. A fluororesin emulsion (1-1) obtained from a fluororesin aqueous dispersion obtained by seed polymerization of an acrylic resin. The above fluororesin emulsion (1-1)
A fluororesin emulsion (1-2) obtained by mixing an acrylic resin into the emulsion. A fluororesin emulsion (1-3) obtained by mixing an acrylic resin with another aqueous dispersion of a fluororesin.

The fluororesin emulsion (1) obtained by mixing the acrylic resin with the fluororesin aqueous dispersion used in the preparation of the above fluororesin emulsion (1-1), which is not seed-polymerized with the acrylic resin. -4).
A fluororesin emulsion (1-5) comprising the other fluororesin aqueous dispersion used in the preparation of the fluororesin emulsion (1-3). A fluororesin emulsion (1-6) comprising the fluororesin aqueous dispersion used in the fluororesin aqueous dispersion (1-1), wherein the acrylic resin is not subjected to seed polymerization.

First, among the above fluororesin emulsions, the fluororesin emulsion (1-1) will be described. The fluororesin emulsion (1-1) is a fluororesin emulsion obtained from a fluororesin aqueous dispersion obtained by seed polymerization of an acrylic resin. The fluorine-containing resin aqueous dispersion can be obtained by forming a fluorine-containing composite resin in an aqueous medium with an acrylic monomer in the presence of the fluorine-containing resin particles. The aqueous medium is not particularly limited, and examples thereof include those obtained by adding an additive or a solvent described in detail below to water.

The fluororesin constituting the above fluororesin particles is a copolymer of fluoroolefin. The fluoroolefin copolymer is dispersed in the form of particles in an aqueous medium, and is polymerized by so-called seed polymerization when a fluorine-based composite resin is formed from the acrylic monomer. In the present specification, “seed polymerization” means a reaction of polymerizing with another monomer in an aqueous medium in which resin particles exist. Accordingly, the fluorine-based composite resin refers to a seed polymer after the seed polymerization, and the resin particles refer to seed particles in the seed polymerization.

Examples of the fluoroolefin include vinylidene fluoride (VdF), tetrafluoroethylene (TFE), and chlorotrifluoroethylene (CTF).
E), hexafluoropropylene (HFP) and the like. Examples of the fluoroolefin copolymer include VdF / TFE copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, TFE / CTFE copolymer, TFE / HFP copolymer, and CTFE / HFP copolymer. Merged, VdF / TFE / CTFE copolymer, VdF / T
FE / HFP copolymer, TFE / CTFE / HFP copolymer, VdF / CTFE / HFP copolymer, VdF / T
FE / CTFE / HFP copolymer and the like can be mentioned.

The fluoroolefin copolymer constituting the seed particles is preferably a VdF-based copolymer, and more preferably a polymer containing 70 mol% or more of VdF. When VdF is 70 mol% or more, the compatibility between the seed particles and the polymer composed of the acrylic monomer is improved.

The average particle diameter of the seed particles is closely related to the average particle diameter of the fluorine-based composite resin after the seed polymerization, and the average particle diameter of the fluorine-based composite resin after the seed polymerization is set to 50 to 300 nm. Therefore, the thickness is preferably set to 40 to 290 nm.

The copolymer constituting the seed particles can be obtained by a usual emulsion polymerization method. For example, 0.01 to 1.0% by weight, based on water, of a fluorine-based reactive emulsifier having a hydrophilic site, and 0 to 1.0% by weight of a fluorine-based emulsifier.
It can be prepared by emulsion polymerization of a monomer mixture containing a fluoroolefin in the coexistence of each of the above components.

Also, 1.0% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight with respect to water.
0.001 to 0.1% by weight, preferably 0.01 to 0.05% by weight, of the nonionic non-fluorine-based interface with respect to the following (the lower limit is usually 0.01% by weight) of a fluorinated surfactant and water. It can be prepared by emulsion polymerization of a monomer mixture containing a fluoroolefin in the presence of an activator. The aqueous dispersion obtained by these methods can stably contain seed particles having an average particle diameter of 0.2 μm or less at a high concentration of 30 to 50% by weight.

Examples of the fluorine-based reactive emulsifier having a hydrophilic site include CF ₂ ＣＦCF— (CF ₂ CF
X) _n3 Y (where X is F or CF ₃ , Y is SO
₃ M, COOM (M is a hydrogen atom, amine, ammonium or alkali metal), n3 represents an integer. ), CF
₂ = CF-O (CFX) _n3 (where X, Y and n3 are the same as above), CH ₂ = CF-CF ₂ -O (CF (C
_{F 3) CF 2 O) n3} -CF (CF 3) Y ( wherein, Y, n
3 is the same as above. _{), CF 2 = CF-CF} 2 -O (C
_{F (CF 3) CF 2 O} ) n3 -CF (CF 3) Y ( in the formula,
Y and n3 are the same as above. And the like, and n3 is preferably in the range of 0 to 3 from the viewpoint of solubility in water and surface activity. More specifically, CF ₂ = CF—CF ₂ —O (CF (CF
_{3) CF 2 O) n3 -CF} (CF 3) the structure of COOH,
Those having n3 of 0 to 2 are used.

The polymerization temperature is from 20 to 120 ° C., preferably from 30 to 70 ° C. When the polymerization temperature is lower than 20 ° C., the stability is lowered. When the polymerization temperature is higher than 120 ° C., the polymerization rate tends to stall due to chain transfer. Although the polymerization depends on the type of the polymer, it is usually 1.0 to 50 kgf / c.
The heating is performed under a pressure of m ² (gauge pressure) for 5 to 100 hours.

Examples of the fluorine-based emulsifier used in the emulsion polymerization of the seed particles include one or a mixture of two or more compounds having a fluorine atom in the structure and having surface activity. For example, X (CF ₂ ) _n3 CO
An acid represented by OH (n3 is an integer of 6 to 20, X represents F or a hydrogen atom) and an alkali metal salt, ammonium salt, amine salt or quaternary ammonium salt thereof; Y (C
_{H 2 CF 2) m3 COOH (} m3 is an integer of 6 to 13, Y
Represents F or a chlorine atom. And the alkali metal salts, ammonium salts, amine salts and quaternary ammonium salts thereof. More specifically,
Examples thereof include ammonium salts of perfluorooctanoic acid and ammonium salts of perfluorononanoic acid.
In addition, a known fluorine-based surfactant can be used.

In the emulsion polymerization for obtaining the seed particles, a small amount of a nonionic non-fluorinated surfactant can be used in the presence of a fluorine-based surfactant, and specific examples thereof include polyoxyethylene alkyl ethers , Polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerin esters and derivatives thereof.

More specifically, examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether and the like. Polyoxyethylene alkyl phenyl ethers include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like, and polyoxyethylene alkyl esters include monolaurate polyethylene glycol, Examples thereof include polyethylene glycol oleate and polyethylene glycol monostearate. Examples of the sorbitan alkyl esters include monolaurin. Examples include polyoxyethylene sorbitan, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like, and examples of glycerin esters include glyceryl monomyristate and glyceryl monostearate. And glyceryl monooleate.

Examples of these derivatives include polyoxyethylene alkylamine, polyoxyethylene alkylphenyl-formaldehyde condensate, and polyoxyethylene alkyl ether phosphate.
Particularly preferred are polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters having an HLB value of 10 to 18, specifically, polyoxyethylene lauryl ether (EO: 5 to 5).
20. EO represents the number of ethylene oxide units. ),
Polyethylene glycol monostearate (EO: 6 ~
10).

The acrylic monomer is not particularly restricted but includes, for example, alkyl acrylates having 1 to 18 carbon atoms in the alkyl group and 1 to 18 carbon atoms in the alkyl group.
And a monomer having an ethylenically unsaturated bond copolymerizable therewith.

Examples of the alkyl acrylate having 1 to 18 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, and the like.
I-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-hexyl acrylate, t-butylcyclohexyl acrylate, stearyl acrylate And lauryl acrylate.

The alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group includes, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-methacrylic acid.
Butyl, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, and the like. .

For the purpose of improving solvent resistance and water resistance, polyfunctional monomers such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be copolymerized. Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate and the methacrylate include the following (I) and (II).

(I) Monomers having a reactive functional group, for example, ethylenically unsaturated carboxylic acids such as maleic acid, itaconic anhydride, succinic anhydride, crotonic acid; acrylamide, methacrylamide, N-methyl Amide compounds such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylolmethacrylamide, N-methylmethacrylamide, N-butoxymethylmethacrylamide; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate , Hydroxyl-containing monomers such as hydroxypropyl methacrylate; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; γ-trimethoxysilane methacrylate, γ-triethoxysilane methacrylate and the like And aldehyde group-containing monomers such as acrolein; caprolactone-modified hydroxy acrylate and caprolactone-modified hydroxy methacrylate.

(II) Other vinyl compounds, for example, α-olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether Alkenyls such as polyoxyethylene allyl ether (POEAE), ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate , Vinyl benzoate, VEOVA9, VEOVA10
Vinyl esters such as (manufactured by Shell); ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride, crotonic acid; styrene, α-methylstyrene, p-ter
aromatic vinyl compounds such as t-butylstyrene; acrylonitrile;

As the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate or methacrylate, a compound containing in its molecule a low molecular weight polymer or oligomer containing a hydrophilic site may be used. it can. The above-mentioned hydrophilic site means a site having a hydrophilic group or a site having a hydrophilic bond, and a site comprising a combination thereof. The hydrophilic group may be any of ionic, non-ionic, amphoteric and combinations thereof, but is preferably a non-ionic or anionic hydrophilic group. Further, a known reactive emulsifier may be used.

Examples of the acrylic acid ester, a monomer having an ethylenically unsaturated bond copolymerizable with the methacrylic acid ester, and the reactive emulsifier include, for example, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate, and polyethylene. Glycol acrylate,
Polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polyoxyethylene alkyl allyl phenyl ether, polyoxyethylene alkyl allyl phenyl Ether sulfate, styrene sulfonate, allyl alkyl sulfonate, polyethylene glycol methacrylate sulfate, alkyl allyl sulfosuccinate, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, polyoxyethylene alkyl phenyl ether acrylic Acid Ether, methacryloyloxy polyoxyalkylene sulfates, methacryloyloxy alkylene sulfates, polyoxyethylene vinyl ethers include polyoxyethylene vinyl esters, and the like.

When the acrylic monomer is subjected to seed polymerization in the presence of the fluororesin particles, first, the swelling of the acrylic monomer into the fluororesin occurs. An aqueous dispersion of the homogeneously dissolved fluorocopolymer is obtained. Thereafter, by adding a polymerization initiator, the acrylic monomer is polymerized to form compatible particles with molecular chains entangled. When the acrylic monomer is polyfunctional, an interpenetrating network (IPN) can be formed. Examples of the polyfunctional acrylic monomer include monoglycol dimethacrylate and diglycol dimethacrylate.

The above-mentioned seed polymerization of the acrylic monomer can be carried out by a known method, for example, a method in which the entire amount of the acrylic monomer is charged into the reaction system in the presence of the fluorine-containing resin particles, Can be carried out by a method in which a part of the above is charged and then the remainder is charged continuously or dividedly, or a method in which the entire amount of the acrylic monomer is continuously charged. Also,
The polymerization conditions for the seed polymerization are the same as those for ordinary emulsion polymerization.For example, in an aqueous medium containing fluororesin particles, a surfactant, a polymerization initiator, a chain transfer agent, and in some cases, a chelating agent, Add pH adjuster and solvent
Polymerization can be carried out by performing the reaction at a temperature of 0 to 90 ° C for 0.5 to 6 hours.

As the above-mentioned surfactant, an anionic, nonionic or anionic-nonionic combination can be used, and in some cases, an amphoteric surfactant can also be used. Examples of the anionic surfactant include higher alcohol sulfates, alkyl sulfonate sodium salt, alkylbenzene sulfonate sodium salt, dialkyl succinate sodium sulfonate, and alkyl anionic surfactants such as alkyl diphenyl ether disulfonic acid sodium salt. In addition to surfactants, fluorinated anionic surfactants such as fluoroalkylcarboxylates, fluoroalkylsulfonates, and fluoroalkylsulfates can be mentioned.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, and glycerin. Esters and their derivatives can be mentioned. Examples of the amphoteric surfactant include lauryl betaine.

As the surfactant, a so-called reactive emulsifier which can be copolymerized with an acrylic monomer can be used. Further, such a reactive emulsifier can be used in combination with the above-mentioned emulsifier. it can. The amount of the surfactant used is usually, per 100 parts by weight of the acrylic monomer,
It is 0.05 to 5.0 parts by weight.

The polymerization initiator used in the seed polymerization is not particularly limited as long as it generates a radical capable of being subjected to a free radical reaction in an aqueous medium at a temperature between 20 ° C. and 90 ° C. It is also possible to use in combination with a reducing agent. Examples of such a polymerization initiator include water-soluble polymerization initiators such as persulfate and hydrogen peroxide, and reducing agents such as sodium pyrobisulfite, sodium hydrogen sulfite, sodium L-ascorbate and Rongalite. it can. As an oil-soluble polymerization initiator, diisopropyl peroxydicarbonate (IP
P), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN) and the like. The amount of the polymerization initiator is usually 0.05 to 2.0 parts by weight per 100 parts by weight of the acrylic monomer.

Examples of the chain transfer agent used in the above seed polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; n-dodecyl mercaptan;
Mercaptans such as dodecyl mercaptan and n-octyl mercaptan can be exemplified. The amount of the chain transfer agent to be used is generally 0 to 5.0 parts by weight per 100 parts by weight of the acrylic monomer.

The above-mentioned solvent is used within a range that does not impair workability, disaster prevention safety, environmental safety, and manufacturing safety, for example, in a range of 20% by weight or less. For example, methyl ethyl ketone, acetone, trichlorotrifluoroethane, Methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, texanol, ethyl acetate,
Butyl acetate and the like can be mentioned. The addition of such a solvent may improve the swellability of the acrylic monomer in the fluororesin particles.

The particle diameter of the fluorine-containing resin particles in the aqueous dispersion is preferably from 50 to 300 nm. More preferably, it is 50 to 200 nm. If the particle diameter is less than 50 nm, the viscosity of the aqueous fluororesin dispersion will increase remarkably at a concentration of 30% or more, which is a practical range, which will hinder the work of coating. When the particle diameter exceeds 300 nm, the sedimentation stability of the obtained fluororesin aqueous dispersion becomes poor, and the resin composition having the same composition causes an increase in the minimum film forming temperature of the fluororesin aqueous dispersion. It will be.
The fluororesin emulsion (1) obtained as described above
In -1), the total amount of the seed-polymerized acrylic resin is usually 10 to 400 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin constituting the seed particles.
９５95 parts by weight.

Thus, the fluororesin emulsion (1-1)
Then, the acrylic resin is mixed with the fluororesin emulsion (1-2) obtained by mixing the acrylic resin with the fluororesin emulsion (1-1), and the other fluororesin aqueous dispersion. Fluororesin emulsion (1-3) obtained by the above method, the fluorinated resin aqueous dispersion used in the preparation of the above fluorinated resin emulsion (1-1), which is not seed polymerized with acryl resin, A fluororesin emulsion (1-4) obtained by mixing, a fluororesin emulsion (1-5) composed of the other fluororesin aqueous dispersion used for preparing the fluororesin emulsion (1-3), and An aqueous dispersion of a fluorine-containing resin used for preparing the above-mentioned fluororesin emulsion (1-1), wherein the acrylic resin is not seed-polymerized. Ranaru fluorocarbon resin emulsion (1
-6) will be described.

First, other fluorine-containing resin aqueous dispersions will be described. The other fluororesin aqueous dispersion constituting the fluororesin emulsion (1-3) has a basic structure in which fluororesin particles are dispersed in an aqueous medium. The fluororesin constituting the fluororesin particles is a fluororesin made of a copolymer of a fluoroolefin and a monomer copolymerizable therewith. The fluoroolefin is not particularly limited, for example,
Vinyl fluoride (VF), vinylidene fluoride (Vd
F), having 2 to 2 carbon atoms such as tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and trifluoroethylene.
About 4 fluoroolefins and the like can be mentioned.

Examples of the monomer copolymerizable with the fluoroolefin include olefins such as ethylene, propylene, and isobutylene; and ethyl vinyl ether (EV).
E), vinyl ethers such as cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, and polyoxyethylene vinyl ether; polyoxyethylene allyl ether;
Alkenyls such as ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9 (manufactured by Shell), VEOVA10 (manufactured by Shell), etc. And ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid.

The copolymer of the above-mentioned fluoroolefin and a monomer copolymerizable therewith is not particularly restricted but includes, for example, CTFE / vinyl ether copolymer, CTFE / vinyl ester copolymer and TFE / vinyl ether copolymer. Coalesce, TFE / vinyl ester copolymer, TFE / ethylene copolymer, TFE / propylene copolymer, CTFE /
Ethylene copolymer, CTFE / propylene copolymer, C
TFE / ethylene / vinyl ether copolymer, CTFE
/ Ethylene / vinyl ester copolymers, and those obtained by modifying those copolymers with a small amount of copolymerizable monomers.

The aqueous fluororesin dispersion is, for example,
After polymerizing the fluorine-containing resin constituting the fluorine-containing resin particles in a solvent or the like, in the presence of an emulsifier, dispersed in water,
A phase inversion method in which the solvent is distilled off, a method in which the emulsion polymerization of the fluorine-containing resin constituting the fluorine-containing resin particles is performed in an aqueous medium, and the like can be given. Preferred is a method in which emulsion polymerization is carried out in an aqueous medium. The emulsion polymerization can be carried out by the same method as the emulsion polymerization usually performed, for example, in a closed container, in an aqueous medium, a surfactant, a polymerization initiator, a chain transfer agent, in some cases a chelating agent, In the presence of a pH adjuster and a solvent, a fluoroolefin, a monomer such as a monomer copolymerizable with the fluoroolefin, is heated at a temperature of 10 to 90 ° C. for 0.5 hour.
It can be obtained by reacting for ~ 40 hours.

As the surfactant, an anionic, nonionic or anionic-nonionic combination can be used, and in some cases, an amphoteric surfactant can also be used. Examples of the anionic surfactant include higher alcohol sulfates, alkyl sulfonate sodium salt, alkylbenzene sulfonate sodium salt, dialkyl succinate sodium sulfonate, and alkyl anionic surfactants such as alkyl diphenyl ether disulfonic acid sodium salt. In addition to surfactants, fluorinated anionic surfactants such as fluoroalkylcarboxylates, fluoroalkylsulfonates, and fluoroalkylsulfates can be mentioned.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, and glycerin. Esters and derivatives thereof can be mentioned. Examples of the amphoteric surfactant include lauryl betaine. Further, a so-called reactive emulsifier can be used as the surfactant, and further, such a reactive emulsifier and the above-mentioned emulsifier can be used in combination.

The polymerization initiator used in the above emulsion polymerization is not particularly limited as long as it generates a radical capable of undergoing a free radical reaction in an aqueous medium at a temperature of 10 to 90 ° C., and in some cases, It is also possible to use in combination with a reducing agent. Examples of such a polymerization initiator include water-soluble polymerization initiators such as persulfate and hydrogen peroxide, and reducing agents such as sodium pyrobisulfite, sodium hydrogen sulfite, sodium L-ascorbate and Rongalite. it can. As the oil-soluble polymerization initiator,
Diisopropyl peroxydicarbonate (IPP),
Examples include benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN), and the like.

Examples of the chain transfer agent used in the above emulsion polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and n-octyl mercaptan. Can be mentioned. The solvent is used within a range that does not impair workability, disaster prevention safety, environmental safety, and manufacturing safety, for example, in a range of 20% by weight or less,
For example, methyl ethyl ketone, acetone, trichlorotrifluoroethane, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, texanol , Ethyl acetate, butyl acetate and the like.

This concludes the description of the other fluorine-containing resin aqueous dispersion. Among the fluororesin emulsions, the fluororesin emulsion (1-3) is obtained by mixing an acrylic resin with the above-mentioned other fluororesin aqueous dispersion.
Further, the fluororesin emulsion (1-2) of the fluororesin emulsion is obtained by mixing an acrylic resin with the fluororesin emulsion (1-1) which has already been described. Furthermore, a fluororesin emulsion (1-4) obtained by mixing an acrylic resin with a fluororesin aqueous dispersion,
It has a basic structure in which the “seed particles” described in detail in the description of the fluororesin emulsion (1-1) are dispersed in an aqueous medium, but the acrylic resin is not seed-polymerized.

As described above, the “seed particles” are made of a copolymer of a fluoroolefin. Examples of the fluoroolefin include vinylidene fluoride (VdF) and tetrafluoroethylene (TFF).
E), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and the like. Examples of the fluoroolefin copolymer include Vd
F / TFE copolymer, VdF / CTFE copolymer, Vd
F / HFP copolymer, TFE / CTFE copolymer, TF
E / HFP copolymer, CTFE / HFP copolymer, Vd
F / TFE / CTFE copolymer, VdF / TFE / HF
P copolymer, TFE / CTFE / HFP copolymer, Vd
F / CTFE / HFP copolymer, VdF / TFE / CT
FE / HFP copolymers and the like can be mentioned, and detailed explanations regarding these have already been given.

The acrylic resin is not particularly limited as long as it is a polymer whose main chain is constituted by a hydrocarbon chain derived from acrylic acid and / or methacrylic acid. And a copolymer of an acrylic monomer and another monomer having an ethylenically unsaturated double bond copolymerizable therewith. The acrylic monomer is not particularly limited as long as it contains acrylic acid and / or methacrylic acid (hereinafter also referred to as “(meth) acrylic acid”). For example, acrylic acid, alkyl acrylate, Examples thereof include methacrylic acid and alkyl methacrylate. The alkyl (meth) acrylate is not particularly limited. For example, the alkyl acrylate has 1 to 18 carbon atoms, and the alkyl group has 1 to 1 carbon atoms.
18 alkyl methacrylate and the like.

Examples of the alkyl acrylate having 1 to 18 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, and the like.
I-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-hexyl acrylate, t-butylcyclohexyl acrylate, stearyl acrylate And lauryl acrylate. The alkyl group has 1 to 1 carbon atoms.
Examples of the alkyl methacrylate of 8 include, for example,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylic acid n-hexyl,
Examples thereof include t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, and the like.

For the purpose of improving solvent resistance and water resistance, a polyfunctional monomer such as ethylene glycol dimethacrylate or propylene glycol dimethacrylate may be copolymerized with the acrylic monomer. Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate and the methacrylate include the following (I)
And the following (II).

(I) Monomers having a reactive functional group, for example, ethylenically unsaturated carboxylic acids such as maleic acid, itaconic anhydride, succinic anhydride, crotonic acid; acrylamide, methacrylamide, N-methyl Amide compounds such as acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylolmethacrylamide, N-methylmethacrylamide, N-butoxymethylmethacrylamide; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate , Hydroxyl-containing monomers such as hydroxypropyl methacrylate; epoxy-containing monomers such as glycidyl acrylate and glycidyl methacrylate; γ-trimethoxysilane methacrylate, γ-triethoxysilane methacrylate and the like And aldehyde group-containing monomers such as acrolein; caprolactone-modified hydroxy acrylate and caprolactone-modified hydroxy methacrylate.

(II) Other vinyl compounds, for example, α-olefins such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether Vinyl ethers such as polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl, VEOVA9, VEOVA10 (manufactured by Shell); itaconic anhydride, succinic anhydride,
Ethylenically unsaturated carboxylic acids such as crotonic acid; aromatic vinyl compounds such as styrene, α-methylstyrene and p-tert-butylstyrene; acrylonitrile and the like.

As the monomer having an ethylenically unsaturated bond copolymerizable with the acrylate or methacrylate, a compound containing in its molecule a low molecular weight polymer or oligomer containing a hydrophilic site may be used. it can. The above-mentioned hydrophilic site means a site having a hydrophilic group or a site having a hydrophilic bond, and a site comprising a combination thereof. The hydrophilic group may be any of ionic, non-ionic, amphoteric and combinations thereof, but is preferably a non-ionic or anionic hydrophilic group. Further, a known reactive emulsifier may be used.

Examples of the above-mentioned acrylic acid ester, a monomer having an ethylenically unsaturated bond copolymerizable with the above-mentioned methacrylic acid ester, and the reactive emulsifier include, for example, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate, polyethylene Glycol acrylate,
Polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol allyl ether, methoxy polyethylene glycol allyl ether, polyethylene glycol polypropylene glycol monomethacrylate, polyethylene glycol polytetramethylene glycol monomethacrylate, polyoxyethylene alkyl allyl phenyl ether, polyoxyethylene alkyl allyl phenyl Ether sulfate, styrene sulfonate, allyl alkyl sulfonate, polyethylene glycol methacrylate sulfate, alkyl allyl sulfosuccinate, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, polyoxyethylene alkyl phenyl ether acrylic Acid Ether, methacryloyloxy polyoxyalkylene sulfates, methacryloyloxy alkylene sulfates, polyoxyethylene vinyl ethers include polyoxyethylene vinyl esters, and the like.

In order to obtain the acrylic resin of the present invention, a homopolymer of the above-mentioned acrylic monomer and a copolymer of the above-mentioned acrylic monomer and another copolymerizable monomer are prepared. The polymerization method is not particularly limited, and conventionally known methods, for example, emulsion polymerization, suspension polymerization, bulk polymerization, and the like can be appropriately selected and used. Also, the molecular weight of the polymer after polymerization can be appropriately selected in consideration of its use.

Further, a polymerization vessel used for polymerization,
As the polymerization method, polymerization initiator, polymerization inhibitor, other auxiliaries, emulsification aids in emulsion polymerization, surfactants, and other additives, conventionally known ones can be appropriately selected and used. In the selection, any conventionally known acrylic resin can be used as long as the obtained acrylic resin is appropriate.

The above fluororesin emulsion (1-2),
The mixing amount of the acrylic resin mixed to form the fluororesin emulsion (1-3) and the fluororesin emulsion (1-4) is preferably 5 to 80% by weight, particularly preferably 10 to 70% by weight. It is. If the mixing amount of the acrylic resin is too low, the film-forming properties of the entire aqueous dispersion will decrease, and the object of the present invention cannot be achieved. If the mixing amount is too large, the weather resistance will deteriorate.

The above fluororesin emulsion (1-2),
The mixing ratio when the above-mentioned fluororesin emulsion (1-3) or the above-mentioned fluororesin emulsion (1-4) and the above-mentioned acrylic resin are mixed in the above-mentioned aqueous medium is not particularly limited. It is preferable to mix them so that the concentration is about 5 to 90% by weight, preferably 20 to 80% by weight. The mixing method is not particularly limited, and a generally known method can be used.

A curing agent may be added to the fluororesin emulsion of the present invention, if desired, for the purpose of further improving the durability and solvent resistance of the coating film formed by the coating composition. As described above, the acrylic resin contained in the fluororesin emulsion may have a functional group, and in such a case, the fluororesin emulsion has a functional group that reacts with a curing agent. ing. The curing agent is not particularly limited, and examples thereof include an isocyanate-based curing agent and a melamine-based curing agent.

As described above, the fluororesin emulsion (1-
Fluororesin emulsion (1-2) obtained by mixing acrylic resin in 1), Fluororesin emulsion (1-3) obtained by mixing acrylic resin in other fluorinated resin aqueous dispersion, and the above fluorinated resin emulsion (1-
The fluororesin emulsion (1-) obtained by mixing the acrylic resin with the aqueous dispersion of the fluororesin used in the preparation of 1), which is not seed-polymerized with the acrylic resin.
The explanation of 4) has been completed. The fluororesin emulsion (1- 1) composed of the other fluororesin aqueous dispersion used in the preparation of the above fluororesin emulsion (1-3)
5) is another fluororesin aqueous dispersion which has already been described. Further, the fluororesin emulsion (1-6), which is the aqueous fluororesin dispersion used for the preparation of the fluororesin emulsion (1-1) and which is obtained by not seed polymerizing an acrylic resin, is a fluororesin emulsion. This is an aqueous dispersion of a fluorine-containing resin before seed polymerization of an acrylic resin, which has already been described in the section of the emulsion (1-1).

The description of the fluororesin emulsion of the present invention has been completed. The fluororesin in the fluororesin emulsion of the present invention is 1 to 50% by weight based on the total solid content of the composition for forming concrete. The fluororesin in the fluororesin emulsion of the present invention means the fluororesin constituting the fluororesin emulsion described in detail above, and the portion of only the resin containing fluorine among the solid content resins in the fluororesin emulsion. Means When the content of the fluororesin is less than 1% by weight based on the total solid content of the concrete forming composition, acid resistance and corrosion resistance tend to be inferior, and non-adhesiveness tends to disappear. %, The strength of the concrete formed tends to decrease.

The fluororesin emulsion of the present invention preferably contains a repellent in a range of 200% by weight or less based on the solid content of the fluororesin. Hereinafter, the repellent will be described in detail.

The repellent used in the present invention is at least one selected from a compound having a perfluoroalkyl group, a fluorinated surfactant, a fluorinated oil, a fluorosilicone oil, and a silicone oil. Among them, compounds having a perfluoroalkyl group are particularly preferred. Hereinafter, these repellents will be described.

(I) Compound Having a Perfluoroalkyl Group A homopolymer of a perfluoroalkyl group-containing ethylenically unsaturated monomer or a copolymer of the same with another monomer can be given. . Examples of the above-mentioned perfluoroalkyl group-containing ethylenically unsaturated monomer include compounds represented by the following formula.

[0081]

Embedded image

In the formula, Rf represents an alkyl group having 4 to 4 carbon atoms.
Represents 20 perfluoroalkyl groups. R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms. R ² represents an alkylene group having 1 to 10 carbon atoms. R ³ represents hydrogen or a methyl group. R ⁴ represents an alkyl group having 1 to 17 carbon atoms. n represents an integer of 1 to 10. m represents an integer of 0 to 10.

Other monomers copolymerizable with the above-mentioned perfluoroalkyl group-containing ethylenically unsaturated monomer include:
For example, alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol di (meth) acrylate, N
-Methylol acrylamide, ethylene, vinyl chloride,
Vinyl fluoride, (meth) acrylamide, styrene,
α-methylstyrene, p-methylstyrene, vinyl alkyl ether having an alkyl group having 1 to 20 carbon atoms, halogenated alkyl vinyl ether having an alkyl group having 1 to 20 carbon atoms, vinyl having an alkyl group having 1 to 20 carbon atoms Alkyl ketone, maleic anhydride, butadiene, isoprene,
Chloroprene; a silyl group-containing vinyl monomer such as vinyltriethoxysilane, vinyltrimethoxysilane,
γ- (methacryloxypropyl) trimethoxysilane and the like can be mentioned. Those obtained by dissolving or dispersing these copolymers in an organic solvent or an aqueous medium are commercially available,
For example, Unidyne TG-652 (made by Daikin Industries), Unidyne TG-664 (made by Daikin Industries),
Unidyne TG-410 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned.

In addition to (I) the polymer having a perfluoroalkyl group, a compound having another perfluoroalkyl group can also be used as the repellent of the present invention. The compounds having the other of the perfluoroalkyl ^{group, RfN (R 1) R 2} -OH Rf (CH 2) n -OH RfCON (R 1) R 2 -OH RfCH 2 C (OH) (R 1) R _{^{2 -OH RfCH 2 C (OCOR 4}} ) H-R 2 -OH RfSO 2 n (R 1) (CH 2) n -OH RfCON (R 1) (CH 2) n -OH RfN (R 1) R 2 - SH Rf (CH ₂ ) n -SH RfCON (R ¹ ) R ² -SH RfCH ₂ C (SH) (R ¹ ) R ² -SH RfCH ₂ C (OCOR ⁴ ) H-R ² -SH RfSO ₂ N (R _{^{1) (CH 2) n -SH}} RfCON (R 1) (CH 2) n -SH RfN (R 1) R 2 -NH 2 Rf (CH 2) n -NH 2 RfCON (R 1) R 2 -NH 2 _{RfCH 2 C (NH 2) (} R 1) R 2 -NH 2 RfCH 2 C (OCOR 4) H-R 2 - ^{_{H 2 RfSO 2 N (R 1}} ) (CH 2) n -NH 2 RfCON (R 1) (CH 2) n -NH 2 ( ^{wherein, Rf, R 1, R 2} , R 4, n , the a The same applies) and a reaction product of an isocyanate compound and the like.

Examples of the isocyanate compound include aliphatic, alicyclic, and aromatic monoisocyanate group-containing compounds. Examples of the polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene triisocyanate, and lysine. Ester triisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate,
Toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and the like; and their modified products include modified trisburet, modified isocyanurate, modified triol, and the like.

Further, as the compound having a perfluoroalkyl group which can be used as the repellent of the present invention, RfN (R ¹ ) R ² —OH Rf (CH ₂ ) n —OH RfCON (R ¹ ) R ² _{-OH RfCH 2 C (OH) (} R 1) R 2 -OH RfCH 2 C (OCOR 4) H-R 2 -OH RfSO 2 n (R 1) (CH 2) n -OH RfCON (R 1) (CH ₂ ) Ester reaction between a compound represented by n-OH (wherein Rf, R ¹ , R ² , R ⁴ and n are the same as described above) and a compound having a carboxylic acid or phosphoric acid as a functional group. Products and the like can be mentioned.

(II) Fluorinated Surfactant The fluorinated surfactant used in the present invention is a surfactant having a perfluoroalkyl group or a surfactant having a perfluoroalkylene group. Examples include a surfactant, a cationic fluorine-based surfactant, an amphoteric fluorine-based surfactant, and a nonionic fluorine-based surfactant. More specifically, Unidyne DS-101 (manufactured by Daikin Industries, Ltd.), Unidyne DS
-202 (manufactured by Daikin Industries, Ltd.), Unidyne DS-30
1 (manufactured by Daikin Industries, Ltd.) and Unidyne DS-406 (manufactured by Daikin Industries, Ltd.). (III) Fluorine-based oil Examples of the fluorine-based oil used in the present invention include polymers of perfluoropolyether and chlorotrifluoroethylene, and other specific fluorinated hydrocarbon compounds. More specifically, Demnum S-20 (manufactured by Daikin Industries, Ltd.) and Daifoil # 20 (manufactured by Daikin Industries, Ltd.) can be exemplified.

(IV) Fluorosilicone Oil The fluorosilicone oil used in the present invention has a fluoroalkyl group on the side chain or terminal of polysiloxane. More specifically, FS-1265 (manufactured by Dow Corning Toray Silicone Co., Ltd.), X-22-8
19 (manufactured by Shin-Etsu Chemical Co., Ltd.) and FL100 (manufactured by Shin-Etsu Chemical Co., Ltd.). (V) Silicone oil The silicone oil used in the present invention is 25 ° C.
And a silicone oil having a reactive group in a side chain or a terminal. More specifically, dimethyl silicone oil, methyl chloride silicone oil, methyl phenyl silicone oil, organically modified silicone oil and the like can be mentioned. For example, compounds represented by the following general formula can be mentioned.

[0089]

Embedded image

In the formula, R ¹² represents an alkylene group having 1 or more carbon atoms. PA represents a polyalkylene oxide.
x and y represent an integer of 1 or more. More specifically, for example, PRX413 (manufactured by Dow Corning Toray Silicone Co., Ltd.), SF8417 (same), SF8418 (same), B
Y16-855B (same), SF8427 (same), SF8
428 (same), X-22-161C (Shin-Etsu Chemical Co., Ltd.), KF-857 (same), KP-358 (same), KP
-359 (same as above).

The content of the repellent contained in the fluororesin emulsion of the present invention is 20 to the fluororesin solid content.
It is preferably 0% by weight or less. 2 repellent content
If it exceeds 00% by weight, it tends to be impossible to form a fluororesin emulsion, and it will not be possible to exhibit acid resistance, corrosion resistance and non-adhesion.

The description of the repellent has been completed. The fluororesin emulsion of the present invention preferably further contains an organosilicon compound in addition to the repellent. Hereinafter, the organosilicon compound will be described.

The organosilicon compound has the following general formula (I):

Embedded image

(In the formula, R ¹ⁿ represents a saturated alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, it may be the same or different. R ²ⁿ has 1 to 5 carbon atoms. And when nn is 2 or more, they may be the same or different. Nn represents an integer of 1 to 9.)
It is represented by The saturated alkyl group having 1 to 18 carbon atoms represented by R ¹ⁿ is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc., which may be linear or branched. Good.

The saturated alkyl group having 1 to 5 carbon atoms represented by R ²ⁿ is not particularly restricted but includes, for example, methyl group,
Examples thereof include an ethyl group, a propyl group, a butyl group, and a pentyl group, and these may be linear or branched. The above nn is an integer of 1 to 20.

More specifically, examples of the organosilicon compound include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane,
Hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyl Trimethoxysilane, hexadecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane , Heptyltriethoxysilane, octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecylt Ethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, hexadecyltriethoxysilane, heptadecyltriethoxysilane, octadecyltriethoxysilane, etc. However, methyltrimethoxysilane and methyltriethoxysilane are preferred.

Further, dimers of the above-mentioned organosilicon compound can also be used as the organosilicon compound used in the present invention.
Wherein nn is 2 and the like. Further, nn may be an integer up to 20.

The above-mentioned organosilicon compound is used after emulsification. Such emulsification can be performed by a conventionally known method, and examples thereof include a method using an emulsifier. The emulsifier is not particularly limited, and examples thereof include a nonionic emulsifier and an anionic emulsifier.

The nonionic emulsifier is not particularly limited. For example, common nonionic emulsifiers include glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan monooleate, sorbitan monotriolate, sorbitan monosesquiolate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene Sorbitan monotriolate,
Polyoxyethylene sorbitan monosesquiolate, polyoxyethylene sorbitol tetraolate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl Examples thereof include phenyl ether, polyoxyethylene nonyl phenyl ether, and polyoxyethylene nonyl phenyl ether.

Further, examples of the nonionic emulsifier include a fluorine emulsifier, a silicone emulsifier and the like. Examples of the fluorine-based emulsifier include those already described in detail in the description of the fluororesin emulsion. Examples of the silicone emulsifier include polyalkylene-modified polydimethylsiloxane compounds represented by the following two general formulas.

[0101]

Embedded image

In the formula, R represents hydrogen or an alkyl group.
m2, n2, a2, b2, c2, d2, and e2 represent integers indicating the number of repetitions. The anionic emulsifier is not particularly limited, and includes, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenylether disulfonate, diethanolamine alkyl phosphate, alkyl Potassium phosphate salt, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene alkyl ether triethanolamine sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate, sodium alkane sulfonate, mixed fatty acid soda soap, semi-hardened cattle fatty acid soda soap, half Hardened beef fatty acid potassium soap, sodium stearate soap, potassium oleate soap, castor oil potassium soap, high-grade soap Sodium cholate sulfate, sodium salt of β-naphthalenesulfonic acid formalin condensate, special aromatic sulfonic acid formalin condensate, special carboxylic acid type surfactant, special polycarboxylic acid type surfactant, special polycarboxylic acid type polymer interface Activators and the like can be mentioned.

The proportion of the anionic emulsifier in the total emulsifier was
Although not particularly limited, 0.01 to 20% by weight is preferable. Any of the above nonionic emulsifiers and any of the above anionic emulsifiers may be used alone or in combination, or may be used in combination with a nonionic emulsifier and an anionic emulsifier. It is preferable to use any of the anionic emulsifiers and any of the anionic emulsifiers in combination. As the nonionic emulsifier, a polyalkylene oxide-modified polydimethylsiloxane and a fluorinated alkyl group-containing polyalkylene oxide are preferable.

The method of emulsifying the organosilicon compound of the present invention using the emulsifier is not particularly limited. For example, water is added to the mixture of the organosilicon compound and the emulsifier while stirring the mixture with a homomixer or the like at a high speed. It can be emulsified by dropping little by little. If the mixture is completely homogeneous after the stirring, a stable emulsified aqueous dispersion can be obtained by adding water. Also, if you add water little by little, the concentration and viscosity will increase at first, insolubles will occur, or it may become a transparent liquid, but as the amount of water gradually increases,
A uniform aqueous dispersion can be obtained.

The content of the organosilicon compound contained in the fluororesin emulsion of the present invention is preferably not more than 200% by weight based on the solid content of the fluororesin. When the content of the organosilicon compound exceeds 200% by weight, the film formation of the fluororesin emulsion is deteriorated, and the acid resistance, the corrosion resistance, and the non-adhesion tend not to be exhibited.

The description of the organosilicon compound has been completed.
The method of mixing the fluororesin emulsion of the present invention with the repellent and / or the organosilicon compound can be performed by appropriately selecting a usual method. For example, stirring is performed using a stirrer such as a homomixer. Can be obtained.

By adding a film-forming aid to the fluororesin emulsion of the present invention, it is possible to form a film sufficiently in other components constituting the concrete forming composition of the present invention. . The film forming aid is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; esters such as ethyl acetate, butyl acetate, dimethyl adipate, and diethyl adipate; benzene, toluene, xylene, and the like. Aromatic hydrocarbons; aliphatic hydrocarbons such as hexane and heptane;
Alcohols such as methanol, ethanol, isopropanol and butanol; halogen-containing solvents such as carbon tetrachloride, methylene dichloride and hexafluoroisopropanol; esters or ethers such as ethylene glycol; "Texanol" (manufactured by Eastman Chemical Company); Plasticizers for aqueous paints and the like can be mentioned.

In addition to the above, the fluororesin emulsion of the present invention may further contain appropriate additives. Such additives are not particularly limited, and include, for example, various inorganic pigments such as titanium oxide, mica, talc, clay, precipitated barium sulfate, silica powder, calcium carbonate, iron oxide, zinc oxide, aluminum powder, and carbon black. Various organic pigments such as azo, phthalocyanine, quinacridone, etc .; plastic pigments; further, wetting agents, thixotropic agents, antioxidants, antifreeze agents, preservatives, antibacterial agents, fungicides, flame retardants, surface conditioning Agents, curing catalysts, viscosity modifiers, leveling agents, ultraviolet absorbers, anti-burr agents, dispersants, and commonly used known additives such as antifoaming agents. Is not particularly limited, and a usual addition amount can be adopted.

For preparing the concrete forming composition of the present invention containing the above-mentioned fluororesin emulsion, various methods can be adopted. For example, first, the above-mentioned cement and the above-mentioned fluororesin emulsion are kneaded, and to this, an aggregate, an admixture, and other additives are added, and water is further added and kneaded; cement, aggregate,
A method of kneading an admixture, other additives, and water at once can be used.

In the above-mentioned kneading, it is necessary to make the respective components uniform by extremely fine kneading since the particles to be kneaded and the specific gravity are various. The kneading is preferably performed mechanically using a mixer used for kneading ordinary concrete, such as a nodular mixer or a forced kneading mixer.

The concrete-forming composition of the present invention can be converted into concrete by a usual method. As such a method, usually, a mold having a desired shape is made of wood or the like, and the above-described concrete forming composition is filled in the mold by carrying, driving, compacting, or the like. Thereafter, the concrete can be obtained by standing and waiting for solidification, while keeping in mind the climate such as the temperature, rainfall and the like.

The concrete-forming composition of the present invention can be used as a concrete structure itself as described above. Considering that the excellent effects of the concrete forming composition of the present invention are mainly exerted at a place where the concrete structure comes into contact with the outside, the concrete forming composition of the present invention It can also be applied by molding over the body. As a method of applying the composition for forming a concrete of the present invention, for example,
On the surface of the concrete structure already constructed,
A method for constructing another concrete molding layer using the concrete forming composition of the present invention; producing a concrete molded product using a normal concrete forming composition other than the concrete forming composition of the present invention; A method of forming the concrete of the present invention with a constant thickness so as to cover the surface portion of the molded article using the concrete forming composition of the present invention; using the concrete forming composition of the present invention on a normal concrete surface And a method of stacking them so as to cover the formed concrete product. With this configuration, even when the concrete structure is large, the center portion does not use a relatively expensive fluororesin emulsion, so that it can be manufactured at a relatively low cost. It is possible to sufficiently exhibit the effect of the above.

The concrete-forming composition of the present invention and concrete using the same have excellent acid resistance, corrosion resistance and non-adhesion, and are useful in the field where these properties can be positively utilized. For example, water treatment facilities such as revetment blocks, cooling introduction waterways, aquaculture tanks, and water storage tanks that are constantly in contact with water; nuclear power generation facilities where durability is extremely important; bathtubs and waterways that come in contact with acidic water such as hot springs; Sidewalks, parks, amusement parks, school yards and pools, and paving blocks to which sticky substances are easily attached; hall roof trusses, hall beams, bridges, railway sleepers, building floors, building walls, building pillars , Roof structures, mineral oil storage tanks, prefabricated garages, prefabricated houses, concrete tiles, U-shaped civil engineering stones, and other molded articles such as body support floors, etc., and applications for covering these surfaces and their surfaces, etc. Can be used as

[0114]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 A pressure-resistant reaction vessel equipped with a stirrer having an internal capacity of 1 liter was charged with 500 ml of deionized water, 0.5 g of ammonium perfluorooctanoate, and 0.05 g of polyoxyethylene monostearate (POE40). After repeated injection and deaeration to remove dissolved air, VdF / TFE
The mixture was pressurized to 10 kgf / cm ² at 60 ° C. with a mixed monomer having a ratio of 74/14/12 mol% of / CTFE. Next, 0.2 g of ammonium persulfate was charged, and VdF / TFE was adjusted so that the pressure in the tank was constant at 10 kgf / cm ^2.
A mixed monomer having a ratio of 74/14/12 mol% of / CTFE was continuously supplied, and the reaction was carried out for 30 hours.

Synthesis Example 2 100 g of the aqueous fluoropolymer dispersion obtained in Synthesis Example 1 was charged into a 200-ml four-necked flask equipped with a stirrer, a condenser, and a thermometer. Succinate alkali salt (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: Eleminol JS2) was added to solid content in an amount of 1.
0% was added. Heat in a water bath with stirring, the tank temperature is 80 ° C
Reached, methyl methacrylate (MMA) 1
A mixed monomer of 3.0 g, 3.5 g of butyl acrylate (BA), and 2.2 g of polyoxyethylene methacrylate (POEMA, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: M90G) was mixed with 0.5 g of an alkyl allyl sulfosuccinate alkali salt.
% Aqueous solution, and this emulsion was added dropwise over 1 hour. Immediately thereafter, 1 ml of a 2% aqueous solution of ammonium persulfate was added to start the reaction. After 3 hours from the start of the reaction, the temperature in the vessel was raised to 85 ° C., maintained for 1 hour, cooled, adjusted to pH 7 with ammonium water, filtered through a 300-mesh wire net, and filtered to give a blue-white aqueous solution of a fluorine-containing seed polymer. A dispersion was obtained. This was used as "emulsion A" in the following experiments.

Synthesis Example 3 An aqueous dispersion of a fluorinated seed polymer was obtained in the same manner as in Synthesis Examples 1 and 2, except that the composition shown in Table 1 was used. This was used as "emulsion B" in the following experiments. Synthesis Example 4 An aqueous dispersion of a fluorinated seed polymer was obtained in the same manner as in Synthesis Example 1 and Synthesis Example 2 except that the composition shown in Table 1 was used. This was used as "emulsion C" in the following experiments.

Synthesis Example 5 A 200 ml stainless steel autoclave equipped with a stirrer was charged with cyclohexyl vinyl ether (CHVE).
17.8 g, polyoxyethylene allyl ether (PO
EAE, manufactured by NOF Corporation, trade name: PKA5003) 4.2
g, ethyl vinyl ether (EVE) 6.1 g, ion-exchanged water 66.1 g, ammonium perfluorooctanoate (emulsifier) 0.3 g, potassium carbonate 0.35 g, sodium bisulfite 0.02 g, ammonium persulfate (initiator) 0 0.08 g, cooled with ice, and pressurized with nitrogen gas to 3.5 kgf / cm ² to degas. This pressure degassing was repeated twice, and after degassing to 10 mmHg to remove dissolved oxygen, 27.5 g of chlorotrifluoroethylene (CTFE) was charged and reacted at 30 ° C. for 12 hours. A combined aqueous dispersion was obtained. This was used as "emulsion D" in the following experiments.

Synthesis Example 6 An acrylic resin aqueous dispersion was obtained in the same manner as in Synthesis Example 2 except that the aqueous fluoropolymer dispersion was not used and had the composition shown in Table 1. This was used as "emulsion E" in the following experiments. The solid content concentration in Table 1 is the solid content concentration (% by weight) in each emulsion.
And the minimum film formation temperature means a value (° C.) obtained by measuring the minimum film formation temperature of each emulsion according to JIS K6828.

Examples and Comparative Examples 20 g of n-hexyltriethoxysilane, 4 g of polyoxyethylene stearyl ether and 0.02 g of sodium laurate were mixed, stirred at a high speed at 1500 rpm, and 80 g of water was gradually added thereto. An emulsion was obtained. This was used as an organosilicon compound. Unidyne TG-410 (manufactured by Daikin Industries, Ltd.) was used as a repellent. Table 2 shows the organosilicon compound, the repellent, and diethyl adipate as a film-forming aid.
The amount (parts by weight) shown in Table 2 was stirred and mixed with 15 parts by weight of the emulsions A to E produced in the synthesis examples and shown in Table 2. The minimum film formation temperature of the above mixture was determined according to JIS K 682.
The measurement was carried out according to No. 8 and shown in Table 2. Cement (commercially available Portland cement) based on the total weight of the above mixture
60 parts by weight and 40 parts by weight of silica sand (aggregate) were blended, and tap water was added to the mixture so that the water-cement ratio became 59% (Table 2 shows the mixing of cement, silica sand and water). The amount was not shown), and the mixture was put into a nodular mixer and mechanically stirred to obtain a concrete forming composition before hardening.

Each of the above concrete-forming compositions was carefully poured into a mold (5 × 5 × 10 cm) made of smooth wood, and kept at a temperature of 35 ° C. in a 50% humidity atmosphere for one week. It was left still. After that, remove the formwork,
While maintaining the temperature at 35 ° C in an atmosphere with a humidity of 50%, 3
After leaving still for a week, test concrete was prepared. Adhesive tape (5 cm wide adhesive cloth tape, manufactured by Nitto Denko Corporation) was applied to the surface of the non-adhesive test test concrete, and then the peel strength (g / g) when the adhesive tape was peeled off using a tensile tester.
cm). The initial non-stickiness was measured immediately after the test concrete was made. Each test concrete was allowed to stand for 30 days while being immersed in a 30% sulfuric acid solution (liquid temperature: 25 ° C.). Then remove from the sulfuric acid solution,
It was thoroughly washed with water and left standing for 7 days in a 50% humidity atmosphere while maintaining the temperature at 35 ° C. Thereafter, a non-adhesion test was carried out in the same manner as described above, and a late non-adhesion test was performed. In addition, the weight at the time of the initial non-adhesion measurement and the time of the latter non-adhesion measurement were measured, and the weight change rate was calculated as [(weight at initial non-adhesion measurement)
− (Weight at the time of measurement of late non-adhesion)] ÷ (weight at the time of measurement of initial non-adhesion) × 100 (%). These are shown in Table 2.
It was shown to. In Table 2, "measurement impossible" means that the measurement was changed to tattered and could not be measured.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

The composition for forming concrete of the present invention comprises:
Since it has the above-mentioned configuration, it has both excellent acid resistance and corrosion resistance, and also has non-adhesiveness, bathtubs and waterways in contact with acidic water, pavement applications where gums and other adhesive substances are easily attached, always It can be applied very well as concrete used for underwater structures that come into contact with water.

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Claims (6)

[Claims] 1. A concrete forming composition containing a fluororesin emulsion, wherein the minimum film forming temperature of the fluororesin emulsion is lower than the temperature at the time of concrete hardening. 2. The concrete forming composition according to claim 1, wherein the content of the fluorine resin in the fluororesin emulsion is 1 to 50% by weight based on the total solid content of the concrete forming composition. 3. The concrete forming composition according to claim 1, wherein the fluororesin emulsion contains a repellent in an amount of 0 to 200% by weight based on the solid content of the fluororesin. 4. The fluororesin emulsion contains 0 to 200% by weight of the organosilicon compound based on the solid content of the fluororesin.
4. The concrete forming composition according to claim 1, wherein the composition is contained. 5. A concrete obtained by curing the concrete-forming composition according to claim 1, 2, 3, or 4. 6. A pavement block obtained by curing the concrete forming composition according to claim 1, 2, 3, or 4.