JP2020109136A - Alumina cement-based paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alumina cement-based coating material using a liquid inorganic material composed of a fluid suspension. SOLUTION: A stabilized aqueous suspension containing the following alumina cement is used as a main component, and an alkaline liquid in which sodium silicate or sodium carbonate or potassium carbonate is dissolved to induce a water-hardening reaction of the suspension is water-hardened. As a reaction inducer, an alumina cement-based two-part paint obtained by separately packaging the main agent and the water-hard reaction inducer. <Ingredients of Main Agent> A) Alumina high content alumina cement having an alumina content of 60% or more with respect to the total weight of the alumina cement 0.5% by weight to 42% by weight B) Blocking agent containing a phosphorus-containing compound 0. 1% by weight to 20% by weight C) Blocking agent different from phosphorus-containing compound 0.3 to 5%, preferably 0.3 to 2.5% D) Water retention agent Others [Selection diagram] None

Description

The present invention relates to an alumina cement-based two-component or one-component coating material containing water-dispersible alumina cement that can be cured at room temperature as a main component.

Generally, "inorganic paints" are not mainly organic resins (resins artificially made such as acrylic, urethane, silicon, and fluorine), but minerals (ceramic or silicon is the main component) as the main component. It refers to the paint.
However, all conventional inorganic paints are inferior in binding force (binder effect) at room temperature and film-forming property only with inorganic materials, so that it is difficult to form a coating film. Contains many resin components with excellent properties.

The present inventors have conducted extensive studies in order to develop an alumina cement-based paint in which most of the components are composed of an inorganic material, and the binding force (binder effect) and the film-forming property do not depend on the organic resin. From an aqueous suspension containing an alumina cement containing a hydraulic binder called a "slurry" (suspension, which is a mixture of minerals and sludge in a liquid), ie a fluid suspension The inventors have come to the idea of using such a liquid inorganic material, and have completed the alumina cement-based coating material of the present invention.

Suitable for such a fluid suspension is EXALT (exalto brand name) manufactured by KERNEOS (France). This EXALT can be said to be an alumina cement floated in water, and since the alumina cement is liquefied, it is not a powder, but if EXALT is used, a paint of liquid alumina cement that has never existed can be made.

The fluid suspension is stabilized by adding a blocking agent (or an inhibitor) to stop the hydration of the hydraulic binder. Known blocking containing phosphorus-containing compounds selected from any compound capable of forming any of these compounds by reacting with at least one metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid and water. Agents have been used to stabilize hydraulic binder-based aqueous suspensions containing alumina cement.
Further, it is possible to use boric acid and borate compounds as the blocking agent.
In general, cement powder has large particles (even if small, 100 to 400 microns) and cannot be applied thinly. On the other hand, liquefying (40 micron) enables a thin coating, and the use of this alumina cement-based coating makes it possible to give various designs to the coated surface.

US Patent Publication No. 2014-0343194

Therefore, an object of the present invention is to provide an alumina cement type two-component type or one-component type coating material using a liquid inorganic material composed of a fluid suspension.
That is, the fluid suspension remains liquid for a period of weeks to months, preferably at least 1 month, more preferably 2 months or more, and most preferably at least 6 months, and That is, it remains a liquid suspension even when stored at a temperature in the range of about 15° C. (room temperature) to 55° C. (high temperature). Of course, it does not separate during storage or transportation.

That is, the alumina cement-based two-component coating material of the present invention comprises a stabilized alumina cement aqueous suspension containing the following alumina cement as a main component of the main component, and sodium silicate that induces a hydraulic reaction of the suspension. Alternatively, an alkaline liquid in which sodium carbonate and potassium carbonate are dissolved is used as a hydraulic reaction inducer, and the main agent and the hydraulic reaction inducer are separately packaged.
<Ingredients of main agent>
A) Alumina cement suspension with a high content of alumina having an alumina content of 60% or more, based on the total weight of the alumina cement aqueous suspension, 0.5% to 42% by weight.
B) Blocking agent containing a phosphorus-containing compound in an alumina cement aqueous suspension 0.1% to 20% by weight
C) A blocking agent different from the phosphorus-containing compound in the alumina cement aqueous suspension, for example, a blocking agent composed of boric acid and a borate compound 0.3 to 5%, preferably 0.3 to 2.5%
D) Water-retaining agent (including organic solvent, resin, etc., which is an organic fiber or porous mineral and has a high water-absorption property and has a function of suppressing evaporation of water)
E) Surfactants (dispersing agents, leveling agents, defoaming/foam suppressing agents, wetting agents, etc.)
F) Viscosity modifier G) Coloring pigment (including functional pigments having performances such as high luster, light interference, heat shielding, and light storage)
H) extender pigment (including fine aggregate and fine aggregate with latent hydraulic reactivity such as blast furnace slag)
I) Antibacterial agent, antiseptic agent, antirust agent

In the alumina cement aqueous suspension which is a main component of the main component of the alumina cement-based two-component coating material of the present invention, the blocking agent containing the phosphorus-containing compound is at least one metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid. And a drug blocking comprising a phosphorus-containing compound selected from any compound capable of forming any of these compounds by reacting with water,
It is also characterized in that the phosphorus-containing compound or boric acid and borate compound is contained in an amount of 0.1% by weight to 20% by weight based on the total weight of the alumina cement.

In the alumina cement aqueous suspension which is the main component of the main component of the alumina cement-based two-component coating material of the present invention, the compound capable of forming metaphosphoric acid, phosphorous acid, phosphoric acid or phosphonic acid is phosphorus pentoxide, pyrophosphoric acid, Tripolyphosphoric acid, aminotrimethylenephosphonic acid, 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, tetramethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, Phosphonic acid pentamethylenediethylenetriamine, host recarboxylic acid, N-(phosphonomethyl)iminodiacetic acid, 2-carboxyethylphosphonic acid, 2-hydroxyphosphonocarboxylic acid, sodium metaborate of boric acid and borate compounds, sodium tetraborate , Disodium sesquioxide octaboron tetrahydrate.

In the alumina cement aqueous suspension which is the main component of the main component of the alumina cement-based two-component coating material of the present invention, the alumina cement has an alumina content of 60% or more based on the total weight of the alumina cement aqueous suspension. Alumina cement having a high content of alumina, which is also characterized in that the relative weight of the phosphorus-containing compound is 0.5 to 20% by weight in the alumina cement aqueous suspension.

In the alumina cement-based two-component coating material of the present invention, the hydraulic reaction inducer for inducing the hydraulic reaction of the main component has high solubility in water containing sodium silicate, sodium carbonate and potassium carbonate, and becomes a highly alkaline aqueous solution. It is also characterized by being made of a substance.
In addition, in the alumina cement-based two-component coating material of the present invention, it is known that sodium silicate which is a hydraulic reaction inducer for inducing a hydraulic reaction of the main component is coordinated to a polyvalent metal ion as an anion in an aqueous solution. Since it is a silicate, it has the effect of suppressing the elution of calcium ions in the body and in the coating film (paint).

In the alumina cement-based two-component coating material of the present invention, the hydraulic reaction inducer for inducing the hydraulic reaction of the main component has free calcium ions that cause the precipitation of efflorescence when made into an aqueous solution. It is also characterized in that it does not use a calcium salt compound that easily reacts or a substance that changes to calcium hydroxide.

In the alumina cement-based one-component paint of the present invention, a stabilized alumina cement aqueous suspension containing the following alumina cement is used as the main component of the main component, and a hydraulic reaction inducer containing sodium silicate as the main component is used. The main agent and the hydraulic reaction inducer are packaged together.
<Main ingredient of main agent>
A) Alumina cement suspension with a high content of alumina having an alumina content of 60% or more with respect to the total weight of the alumina cement aqueous suspension, 0.5% to 42% by weight.
B) Blocking agent containing a phosphorus-containing compound in an alumina cement aqueous suspension 0.1% to 20% by weight
C) Blocking agent different from phosphorus-containing compound in alumina cement aqueous suspension 0.3-5%, preferably 0.3-2.5%
D) Water-retaining agent (including organic solvent, resin, etc., which has a high water absorption property, organic or inorganic fiber or porous substance, and has an action of suppressing evaporation of water)
E) Surfactants (dispersing agents, leveling agents, defoaming/foam suppressing agents, wetting agents, etc.)
F) Viscosity modifier G) Coloring pigment (including functional pigments having performances such as high luster, light interference, heat shielding, and light storage)
H) extender pigment (including fine aggregate and fine aggregate with latent hydraulic reactivity such as blast furnace slag)
I) Antibacterial agent, antiseptic agent, antirust agent

The effects of the alumina cement-based paint of the present invention will be described in detail below.
1) Alumina cement, which is the main material (main component), can be used as a liquid with the different performance from general cement. (Normally, powdery hydraulic reactive substances such as Portland cement cannot be made liquid for a long time, and even if it is a solidified product that is hardened by normal use, it has fire resistance, early strength, corrosion resistance, etc. Performance, chemical resistance, etc. cannot be expected.)
a. The strength of a solidified alumina cement (a pencil hardness of about 4H or more) can be achieved simply by mixing it with a liquid hydraulic reaction inducer at room temperature without applying heat unlike a resin. As described above, although the strength development of alumina cement is large, the strength development is difficult in the case of resin-based paint unless heat is applied.
b. Since the main material (main component) is alumina cement, the strength of the inorganic material is exerted, and a super durable paint (coating film) can be formed.
c. Since the main component is alumina cement, it has salt-barrier properties, and is suitable for finishing to structures in areas where salt damage occurs and areas where frequent use of antifreeze (calcium chloride) is sprayed in cold weather.
d. Ordinary Portland cement is weak against acid, but alumina cement is strong against acid and can prevent neutralization of concrete due to the effects of acid rain, CO ₂ gas, NOx gas and SOx gas.
e. Since the main component is alumina cement, it is not affected by ultraviolet rays (UV) and keeps a good coating for a long time.
f. Alumina cement has high abrasion resistance, so if a coating film is formed by coating it on the wall surface that is constantly exposed to sand dust with wind, it will be less likely to be scratched and dirt caused by dust adhesion (cutting into the coating film) Can be prevented.
g. Since the main component is alumina cement, there is no burning by open flame. Therefore, since the coating film does not ignite due to the occurrence of fire, it is possible to prevent the fire from spreading from the coating film.
h. Unlike organic resin-based paints, which are composed mostly of organic substances, they are composed of inorganic components that are difficult to burn and do not gasify even under high heat, so paints and coatings that do not generate gas even when exposed to high temperatures can be made. ..
i. Ordinary Portland cement finishes have a short pot life (about 1 to 2 hours at room temperature) after adding water and are poor in workability, but the alumina cement-based two-component paint of the present invention is acceptable. The working time is the same as the working time (8 hours or more) of the commercially available two-component reaction curable paint, so workability is good.
In addition, by limiting the alkaline curing agent composition that induces the hydraulic reaction to sodium silicate, a one-component type coating that is easy to work in the field and prevents mistakes in mixing the main agent and the curing agent (forgetting to put the curing agent) realizable.
j. Phosphoric acid compounds have a reducing action (antioxidant action), and shelf acid has a bactericidal action.
Furthermore, it forms a complex by coordinating with the iron ion of the phosphate compound and delays the elution (corrosion) of the metal, and red rust (ferric oxide is black rust (ferric tetroxide Fe ₃ It has a reducing effect of changing to O ₄ ), which not only contributes to the storage stability of the coating material but also imparts rust prevention to the coating film performance after film formation.
In view of the above action, it exerts a role as a preservative that suppresses the decay of organic compounds such as water contained in the paint for a long period of time.
Further, it also has an effect of suppressing discoloration (rust) due to derivation of a trace amount of iron contained in the mineral-based powder such as the fine aggregate and extender pigment of natural origin mixed in the paint.

2) Since the paint can be made with liquid, it is not necessary to agitate the cement-containing powder with water on site. Of course, by liquefying, it is possible to obtain a predetermined composition simply by stirring with a hand mixer on site.
On the other hand, when the inorganic material is powder, it is necessary to stir with a mortar mixer (large or heavy), dust is generated in the powder, and water must be measured, which imposes a heavy burden on craftsmen.
3) Liquid paints can be colored with liquid pigments in the factory and accurate colors can be obtained. If the paint is a powder, it is difficult to disperse the pigment because powder pigments are added and used at the construction site for coloring, and accurate coloring takes a very long time. Moreover, powder pigments are usually difficult to disperse, and even when premixed in the factory, if the mixing time is short, poor dispersion of color pigments or aggregated pigments cannot be understood, and thus streaking of pigments occurs during construction and stirring. The color may change over time. On the other hand, a liquid paint does not have such a problem, and a stable color can be obtained by easy stirring.
4) Conventional paints containing organic resin as a main component cannot be applied if the water content of the coating base is high or the alkalinity is high, or if the work environment is under high humidity. The alumina cement-based coating material of the present invention can be applied under the conditions as described above, and can be formed into a coating film that is finished without any problems in terms of design and has sufficient performance.
5) The alumina cement-based coating material of the present invention can obtain high hardness and high strength even in a coating film cured at room temperature, but it has the property of further increasing hardness and strength when heat is applied. By utilizing this property, it becomes possible to develop hardness and strength, which were previously impossible, to industrial products that use conventional organic resin-based paints composed of mostly organic substances. Applicable. In particular, the conventional, organic resin-based paint composed of almost organic substances, where the heating of several hundred degrees Celsius is required to obtain high hardness and high strength, the alumina cement-based paint of the present invention has a temperature of less than 100 degrees Celsius. High hardness and high strength can be obtained by heating. From the above, the utility value is high as an industrial paint as well as in terms of performance and energy saving.

Silicates coordinate to polyvalent metal ions (calcium ion, iron ion, aluminum ion, etc.) as anions such as orthosilicate ion (SiO ₄ ⁴ ) and pyrosilicate ion (Si ₂ O ₇ ⁶ ) in aqueous solution, It shows the characteristics of forming a structure.

Embodiments of the two-component alumina cement-based coating material of the present invention will be described in detail below with reference to examples.
The alumina cement-based two-component coating material of the present invention is an aqueous dispersion of alumina cement, which contains, as a main component of the main component, a water-dispersible alumina cement that induces a hydraulic reaction in the presence of an alkaline aqueous solution.
The alumina cement is also called fused cement, slag (cement) cement, or lime-alumina cement, which is a cement produced by mixing and crushing limestone and bauxite, or shale (shale). Compared with other cements, it can obtain strength early and is used for urgent construction work. Although the 1-day strength expresses the strength equivalent to 28 days of that of ordinary Portland cement, the strength is slightly increased thereafter, and the long-term strength may decrease depending on curing conditions. It has characteristics such as withstanding high temperatures of 1000°C or more, but it is expensive, so it is not suitable for general applications, and it is suitable for special applications such as when early strength is required and fire resistance.

In the alumina cement aqueous suspension, which is the main component of the main component of the alumina cement-based two-component coating material of the present invention, at least one metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid, boric acid and water are used as the blocking agent. And a borate compound selected from any compound capable of forming any of these compounds by reacting with.
The blocking agent contains a phosphorus-containing compound in an amount of 0.1 wt% to 20 wt% based on the total weight of the alumina cement and/or calcium sulfoaluminate cement. Can be generated.

In the alumina cement aqueous suspension, which is the main component of the main component of the alumina cement-based two-component coating material of the present invention, the metaphosphoric acid, phosphorus, Compounds capable of forming an acid, phosphoric acid, phosphonic acid or boric acid include phosphorus pentoxide, pyrophosphoric acid, tripolyphosphoric acid, aminotrimethylenephosphonic acid, 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, Ethylenediaminetetramethylenephosphonic acid, tetramethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, phosphonic acid pentamethylenediethylenetriamine, host recarboxylic acid, N-(phosphonomethyl)iminodiacetic acid, 2-carboxyethylphosphonic acid, 2-hydroxy It can be selected from phosphonocarboxylic acid, boric acid, sodium metaborate, sodium tetraborate, disodium trioxide octaboron tetrahydrate.

By reacting the at least one phosphonic acid and metaphosphoric acid, phosphorous acid, phosphoric acid, boric acid with water, any compound that can form any of these compounds includes a carboxylic acid. .. The carboxylic acid is preferably an amino acid such as citric acid, tartaric acid or aspartic acid (more selected and can be selected from mineral acids such as and salts thereof, eg glutamic acid), mandelic acid, humic acid. Acid, fulvic acid, quinic acid.
Of course, at least one selected from any compound capable of forming any of these compounds by reacting the at least one phosphonic acid, boric acid, metaphosphoric acid, phosphorous acid, phosphoric acid with water. There is a combination of one compound and at least one carboxylic acid.

The alumina cement aqueous suspension may further contain a blocking agent different from a phosphorus-containing compound such as a carboxylic acid.
Such a blocking agent may be added in an amount of 0.3 to 5%, preferably 0.3 to 2.5%, based on the total weight of the alumina cement aqueous suspension.
The aqueous alumina cement suspension can also further comprise a blocking agent different from the phosphorus-containing compound, in which case the amount of phosphorus-containing compound is minimal even in the presence of the additional blocking agent. Good.

Furthermore, in the aqueous suspension of the present invention, the minimum optimum amount of the phosphorus-containing compound in order to obtain good stability is inversely proportional to the alumina content in the hydraulic binder or the alumina cement and/or the calcium sulfoaluminate cement. It is supposed to do. It was also found that the stabilization of alumina cement having a high alumina content continued for 6 months or more even when the alumina cement aqueous suspension was stored at 50°C.

In the alumina cement-based two-component coating material of the present invention, the stabilized alumina cement aqueous suspension is a high alumina content alumina cement having an alumina content of 60% or more based on the total weight of the alumina cement. The suspension contains the phosphorus-containing compound and/or the borate compound in a relative weight of 0.5 to 20% by weight.

Metaphosphoric acid 3 (CAS registration number: 37267-86-0), orthophosphoric acid, phosphorous acid (numeral 2) called a compound of number 1, phosphoric acid of number 1, phosphoric acid of number 3: HP (=O), And any of their P-hydrocarbyl derivatives, including any compound capable of reacting with water to form any of these compounds.



In addition, as a compound capable of forming any of these compounds by reacting with water, metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid, and hydronium ion (which can be formed in contact with H) can be formed. (Which can correspond to compounds) and phosphoric acid, which can be converted into metaphosphoric acid by contact with water.

Further, the following compounds that may be hydrolyzed to phosphoric acid may be mentioned.
For example, it can be hydrolyzed to phosphorus pentoxide or phosphoric anhydride of formula 4, diphosphoric acid, pyrophosphoric acid called a compound of formula 1, tripolyphosphoric acid of formula 5, or phosphoric acid.
Anhydrous phosphoric acid


In addition, as the blocking agent different from the phosphorus-containing compound, as the boric acid and borate compound of the formula 6, sodium metaborate of the formula 7, sodium tetraborate of the formula 8 and disodium trioxide octahydrate of the formula 9 can be used. Examples thereof include boron tetrahydrate.

Also, as demonstrated in the examples below, phosphorus-containing compounds and/or borate compounds act as blocking agents. Thus, it blocks at a relatively low dose to block the dissolution of the alumina cement-based aqueous suspension of alumina cement. By using such a blocking agent, the alumina cement aqueous suspension is stable for a long period (one month or more) and exhibits an effect even at a relatively high temperature (for example, 50° C.).

The phosphorus-containing compound as the blocking agent can also significantly lower the pH value of the alumina cement aqueous suspension. Preferably, the pH value is desirably less than 9, preferably greater than or equal to 7 and less than 8, especially less than 6.5, in order to obtain a stabilized alumina cement aqueous suspension.

In particular, in the case of alumina cement or cement with high alumina content, the relative weight of the phosphorus-containing compound and/or borate compound with respect to the total weight of the required alumina cement is to obtain a life of at least 6 months. It is believed that about 1-10% is required.
Also, the alumina-rich alumina cement used according to the present invention has an alumina content in the range of 65% to 75%, more preferably 68% to 72% with respect to the total weight of the alumina cement. Is desirable.

Desirably, the chemical composition of alumina and high alumina cement contained in the alumina cement is any of the following.
Al ₂ O ₃ : >60%, preferably 60-75%,
CaO: >25%, preferably 25-50%,
SiO ₂ : <5%, preferably <4%, more preferably <2%
Fe ₂ O ₃ : <10%, preferably <5%, more preferably <1%
In the present invention, the hydraulic binder may further contain calcium sulfate. The calcium sulfate can be derived from a compound selected from anhydrous or hemihydrated gypsum, gypsum, or mixtures thereof.
The alumina cement aqueous suspension may contain 0 to 50%, preferably 5 to 30% of calcium sulfate, based on the total weight of the alumina cement aqueous suspension.

In the present invention, the combined use of the above-mentioned alumina cement and calcium sulfate can form a binder for ettringite.
The ettringite is, SO ₄₂ - to and H ₂ during cement hydration O is present, aluminate phase (tricalcium aluminate, 3CaO · Al ₂ O ₃₎ and SO ₄₂ - and H ₂ O are reacted, is generated Refers to a hydrate. The formula represented by the _{3CaO · Al 2 O 3 · 3CaSO} 4 · 32H 2 O.

The alumina cement aqueous suspension used in the present invention may contain additional additives such as a water retention agent. These additives are preferably not only selected from water retention agents, dispersants, rheology agents and bactericides, but can also include plasticizers, antifoams and thickeners.
Further, as a dispersant suitable for use in the alumina cement aqueous suspension, there is Sokalan (registered trademark, manufactured by BASF Japan Ltd.) and the like, and the compounding ratio is 0.1% of the total weight of the alumina cement aqueous suspension. ˜3%, preferably 0.5 to 1%, or 0.1 to 5% by weight of the total weight of the hydraulic binder, preferably 0.6 to 1.8%.

The superplasticizer is preferably selected from clays (xanthan gum such as bentonite, welan gum), starch-derived ethers, guar-derived ethers, polyacrylamide, carrageenan, agar, or organic products such as mineral products, even in mixtures thereof. Good.
The blending ratio of the superplasticizer is 0.1 to 1%, preferably 0.25 to 0.5% of the total weight of the alumina cement aqueous suspension, or 0.2 to 2 of the total weight of the hydraulic binder. %, preferably 0.25 to 1.4%.

Antibacterial or biocide agents include compounds of the isothiazolinone family, such as methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and combinations thereof.
The blending ratio of the antibacterial agent or biocide is 0.005-0.1%, preferably 0.001-0.02% of the total weight of the alumina cement aqueous suspension, or the total weight of the hydraulic binder. It is 0.01 to 0.2%, preferably 0.02 to 0.04%.
Of course, the antibacterial agent or the biocide may include a photocatalytic reaction substance such as titanium oxide, a metal ion such as silver ion, or the like.

Superplasticizers are composed of polyphosphonates, highly polymerized polyethylene glycols, polycarboxylates, highly polymerized polyethylene glycol PCPs and polyacrylates or copolymers of acrylic acid and alkoxy-acrylic acid, and mixtures thereof.

The alumina cement aqueous suspension of the present invention may contain an organic resin. Therefore, it may be used as a bonding composition containing the aqueous alumina cement suspension and at least one organic resin.
Preferably, the binding composition may comprise 0 to 90% organic resin of the alumina cement aqueous suspension.
Such organic resins are preferably polymeric resins, including latex-type polymers and copolymers.

The aqueous alumina cement suspension of the present invention may include fillers to form other compositions.
Such fillers can be selected from minerals or essentially organic and siliceous compounds, such as blast-furnace slags, carbonate compounds (calcium carbonate, dolomite), pigments, titanium oxide, light-reflecting substances such as perlite or vermiculite. There are fillers (sand, quartz, fumed silica).
And the filler is 10% to 30%, preferably 1 to 50% of the total weight of the composition, the remainder being formed from the aqueous alumina cement suspension.

In order to initiate the setting of the alumina cement aqueous suspension or the binding composition, the pH adjusting agent should be only 7 (above this value, preferably higher than the higher pH value, and higher than 9 the pH of the medium). The need to add more to increase the value, which is faster), is to regulate the deblocking reaction, thus blocking the reaction of the additional lithium source with the alumina or calcium sulfoaluminate cement as needed. To do.

Possible combinations in the pH adjusting agent are lithium, lithium hydroxide and lithium sulphate or carbonate or sodium and sulphate or carbonate such as fluorinated slaked lime.
In another combination, sodium hydroxide or potassium hydroxide or sodium aluminate is combined with a promoter, such as lithium or sodium or potassium salts, especially in the form of sulfates, carbonates, chlorides or fluorides, It can be used as a regulator.

Next, a method for producing the above-described alumina cement aqueous suspension will be described. The method comprises successively taking the following steps.
As a first step, water was introduced into the mixing tank, and a blocking agent consisting of a phosphorus-containing compound was stirred while stirring at a speed of 600 rpm or more, preferably at a higher speed of 800 rpm, more preferably at 1000 rpm with a stirrer equipped with an agglomeration prevention blade. Add and add one or more dispersant(s) until dissolution is complete.
Also, gradually maintain the agitation while adding one or more hydraulic binder(s), increase the agitation speed to 1000 rpm or more, preferably 3000 rpm, and optionally other ingredients, such as optionally 1 One or more superplasticizers and bactericide(s) were added and stirred, preferably for 10-15 minutes, for at least 5 minutes.

If the alumina cement aqueous suspension is added with an organic resin forming a bonding composition, the organic resin is added directly at the end of the preparation of the alumina cement aqueous suspension or afterwards by mixing at 600 rpm. It
In this method, any one of these compounds can be formed by reacting one or several kinds selected from metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid, boric acid and the like with water. The blocking agent consisting of at least one phosphorus-containing compound selected from any compounds is based on the total weight of the alumina cement aqueous suspension of alumina cement and/or calcium sulfoaluminate cement added as described above. %, preferably 0.1 to 15%, more preferably 0.3 to 10%, particularly preferably 0.1 to 10% by weight.

The mixing conditions, as well as the order of introduction of the components, can substantially improve the quality of the alumina cement aqueous suspension, preferably the components are mixed together in the following order.
1) solvent 2) blocking agent 3) dispersant 4) cement 5) superplasticizer 6) biocide

That is, the procedure for mixing the above materials is as follows.
1) When a necessary amount of water is introduced into a mixing tank (bowl), stirring is performed at a blade rotation speed of 1000 rpm in a stirrer equipped with a blade at an upper position, and a blocking agent (or inhibitor) is added to the blocking agent ( Mix until up to 3 minutes) dissolve.
2) In addition to the dispersant, one or more hydraulic binder(s) was added to optimize the dispersion, during which the blade was placed on the surface of the alumina cement aqueous suspension. , Mix with the blade in this upper position for about 1 minute.
3) Then, increase the rotation speed to 3000 rpm, add the last component, and lower the blade to the lower position to mix at high speed for 15 minutes. The mixer is then turned off and the walls of the mixing tank as well as the blades are rubbed to remove residual deposits.
These manufacturing conditions are effective to homogenize the efficiently dispersed aqueous alumina cement suspension.

4) Stabilize by adding a blocking agent to the alumina cement aqueous suspension or mineral slurry.
Then, the pH value is measured and stable monitoring is performed.
Measuring pH values in this way is a good way to monitor the stability of aqueous alumina cement suspensions. Aqueous suspensions stabilized with blocking agents are considered unstable when their pH value increases significantly and/or reaches a pKa of (pKa value=9.2). From this value, the setting of hydraulic pressure is started.

Reference table

In the room temperature environment, the initial pH of the slurry 1 gradually increases to the range 8<pH<threshold value 9, but it is stable for several months.
By contrast, at a temperature of 50° C. such a mechanism is clearly accelerated. In fact, an increase in pH value can be observed from the very first day of storage, a threshold of 9, achieved after 30 days, slurry 1 achieved on day 32 when stored at room temperature. , Storage times for stabilized slurries easily exceed 6 months. In contrast, changing the storage conditions (temperature=50° C.) immediately reduces the accumulation time significantly.

In a room temperature environment, the initial pH of Slurry 2 gradually rises, and when observed within a period of 10 days thereafter, the pH value stabilizes at about 6.4, at which value the slurry is completely stable.
Even at a temperature of 50° C., the pH value is very constant, centered on values in the pH unit range of 5-6. For example, Slurry 2 is completely stable after 45 days of storage at 50°C during the observation period.
The results showing pH monitoring performed during the last month at 40 to 50°C indicate that the slurry condition and the pH value do not change. Therefore, when it is stored at 50° C., it is completely stable even after 6 months.

When phosphoric acid is used as a stabilizer, the amount of phosphoric acid may be reduced to less than 0.5% based on the total weight of the alumina cement aqueous suspension while maintaining an appropriate stabilization time at 50°C. You can observe what you can do.
Various "Ettringite slurries" were obtained by varying the sulfate rate and the type of sulfate used.
The stabilization system used is phosphoric acid dosed at 1.2% based on the total weight of the alumina cement aqueous suspension. The proportion of hydraulic binder in the aqueous alumina cement suspension is 60% by weight, based on the total weight of the aqueous alumina cement suspension.
In monitoring the pH value, it can be confirmed that the ettringite-based slurry is completely stabilized with phosphoric acid.

Next, a composition based on a combination of an alumina cement aqueous suspension and an organic resin was prepared. In these examples, slurries 1 and 2, and one organic resin of phosphoric acid and latex type are used by being stabilized.

The composition was stored at 50° C. and pH was measured periodically. After a period of 28 days of storage at 50° C., the composition, which can be observed as the only composition, has a pH below 9.2 and thus keeps it at a completely stable value. All other compositions are based on suspensions stabilized before day 28, thus the range of stability of the mixture is significantly reduced, up to 20% of the weight of the slurry. It is possible to introduce.

When stored at room temperature, the storage time for slurries stabilized with blocking agents such as boric acid easily exceeds 6 months. In contrast, changes in the chemical environment significantly reduce the accumulation time.
In order to see the stability of the composition at 50°C, the composition was stored at 50°C and the pH value was measured periodically.

The results obtained show very stable pH values in the range of pH units from 5 to 7 days from 40 days onwards. During this time there was no change observed for any of the mixtures.
In conclusion, compared to the slurry, which storage temperature, slurry chemical environment, phosphoric acid showed and stabilized with very good results.
Alumina cement aqueous suspensions based on other alumina cements are also inspected.

Next, stability monitoring will be described.
The slurry was observed to change pH as a function of time (days) at 50°C. For slurries based on alumina cement (6,7), by calculating the proportion with 3.5% or 7% (2.5% or 5% relative to the amount of hydraulic binder, alumina cement aqueous suspension). The ratio of the dose of phosphoric acid used according to the suspension was stable, and the pH was stable for 2 months (60 days). As a control, it can be observed to use a 2.5% or 5% slurry based on an alumina cement based aqueous suspension, a dose of phosphoric acid depending on the alumina cement aqueous suspension ( That is, by calculating a ratio of 3.5% or 7% (as a ratio of the amount of hydraulic binder), it affects the slurry stability. As for the ratio of the amount of hydraulic binder, at a dose of 7%, good stability of the slurry could be observed for 1.5 months (45 days). In conclusion, when using phosphoric acid as the blocking agent, these slurries can be stabilized over a period ranging from 20 days to 2 months, depending on the phosphoric acid dosage and the type of alumina cement associated with it. I understand.

As the blocking agent, a combination with phosphonic acid, phosphoric acid, carboxylic acid, that is, citric acid is used.
In the above example, changes in pH as time (days) at 50° C. were observed. pH monitoring shows a very slight rise in pH level that stopped at day 25, the first region corresponding to a subsequent slow rise in pH level due to the onset of slurry destabilization. However, when using a combination of three blocking agents, it could be observed that good stability was obtained with the system for about 45 days at 50°C.
The above is the description of EXALT (trade name) manufactured by KERNEOS (France), which is an alumina cement aqueous suspension that is a main component of the main agent (agent A) of the alumina cement-based two-component coating material of the present invention. It is different from the alumina cement-based two-component paint (two-component hydraulic reactive inorganic paint (Note)) mentioned in the invention.
Note) When the present invention is classified by the "Japanese Industrial Standards" from the form of the conventional finishing material and the required performance, it differs because the main raw material is alumina cement. Specifies the weather-resistant topcoat paint for buildings (hereinafter referred to as paint) used for coating.This standard uses fluorine resin, silicone resin or polyurethane resin as the main raw material, and mixes the main agent and the curing agent to cure. JIS K 5658, which is said to be applied to paints, is similar to JIS K 5658 architectural weather-resistant topcoat paint, and it is a cement-based architectural finishing material handled by the Japanese Industrial Standards JIS A6916 and JIS A6909. Different materials (two-component hydraulic reactive inorganic paint).

The present invention provides a main agent (agent A) containing the alumina cement aqueous suspension described above as a main component, and a hardening agent (agent B) comprising a hydraulic reaction inducer that induces a hydraulic reaction of agent A. Thus, the alumina cement-based two-component coating material of the present invention is formed.
In the production of the alumina cement-based two-component coating material of the present invention, the blocking agent, additive (dispersant, fluidizing agent, plasticizer, antifoaming agent, additive, etc.) used in the above-mentioned alumina cement aqueous suspension is used. It is possible to add additional agents such as sticky agents, water retention agents, biocides, fillers, resins, etc., but in order to impart properties and performance as a paint, it is necessary to use the following methods. , I will explain it later.

First, a detailed description of the curing agent (B agent) comprising the hydraulic reaction inducer of the alumina cement-based two-component coating material of the present invention is given below.
<Selection of alkalinity-imparting substance (hardening agent) and adjustment of hardening agent (painting)>
EXALT 60H (trade name of EXZALT 60H), an aqueous alumina cement suspension manufactured by KERNEOS (France), is a stable fluid (slurry) liquid in the turbid state without hydraulic reaction.
Therefore, a substance that induces a hydraulic reaction is required.
According to the technical data and views of the manufacturer KERNEOS (France), the hydraulic reaction is induced by an alkaline stimulus.
As a "hydraulic reaction inducer" that gives an alkaline stimulus, the manufacturer recommends an aqueous sodium hydroxide solution, but it is not preferable to handle sodium hydroxide, which is a deleterious substance, in the manufacturing process, let alone However, it cannot be used at the painting site.
In particular, the product of the present invention uses a main agent containing an alumina cement turbid solution (EXALT 60H) as a main component and an alkaline liquid that induces a hydraulic reaction of the alumina cement turbid solution, and the main agent and the curing agent are packaged separately. Since it is assumed that the on-site prepared two-component paint is used, the alkaline curing agent (hydraulic reaction inducer) will be directly touched by the worker, which is an unsuitable work in terms of occupational safety.
In addition, since aluminum building materials that are weak in alkalinity are often used in buildings, it is necessary to use an alkaline hardening agent (hydraulic reaction inducer) that does not attack (corrosion) these building materials. ..
Further, as a substance exhibiting alkalinity, it is natural that a substance that does not ionize calcium, which is a causative factor of efflorescence, is desirable.
Therefore, the alkaline curing agent (hydraulic reaction inducer) must be an alkaline liquid containing no calcium salt.

Regarding not only the viewpoint of hydraulic reaction induction of alkaline substances that are present in the world, but also from the perspective of providing excellent coating performance and designability with a safe and harmless paint in a simple operation. The following substances were selected and examined to solve the above-mentioned problems.

1) Confirmation of safety
The presence/absence of danger was evaluated based on the concentration adjustment work in Table 1 and the presence/absence of legal regulations.
* Even if sodium hydroxide, potassium hydroxide, and ammonia, which are designated as deleterious substances under the Poisonous and Deleterious Substances Control Law, have the effect of the invention, the present invention is intended for the on-site preparation of agents A and B Then, it cannot be commercialized from the viewpoint of the Industrial Safety and Health Law.

2) A substance which is alkaline and does not attack aluminum (does not corrode). For comparison with an aqueous solution described in Table 1, a slurry liquid obtained by adding 10 parts by weight of water to 20 parts by weight of ordinary Portland cement is used. The aluminum plate (A1050) without surface treatment was brought into contact with an aluminum sash frame having a sulfuric acid anodized film in spots, and the appearance change after 24 hours was observed.
Evaluation criteria
◯: No change Δ: Slightly discolored ×: Discolored XX: Dissolved

*Sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia are not suitable as the curing agent (hydraulic reaction inducer) of the present invention because they have a high risk of attacking (corroding) aluminum.

3) Hydraulic reaction inducing ability of alumina cement aqueous suspension containing hydraulic binder The above-mentioned 1) confirmation of safety and 2) evaluation result of a substance exhibiting alkalinity that does not attack (do not corrode) aluminum Therefore, sodium silicate containing sodium carbonate, potassium carbonate, and water glass was evaluated as an alkaline liquid that induces a hydraulic reaction of the alumina cement aqueous suspension. As a comparative example, ammonia, sodium citrate, and ordinary Portland cement are added.
Evaluation procedure (1) A sample was prepared by adding the above alkaline solution to an aqueous alumina cement suspension (EXALT 60H) manufactured by KERNEOS and mixing them using a tabletop disper.
(2) A partition is made on a glass plate using a duct tape, and a sample having a volume of a wet film thickness of 500 μm (theoretical dry film thickness of about 150 μm) is poured into the sample, and the temperature is 20 to 25° C. and the relative humidity is 40 to 40° C. Leave it indoors at 60%.
(3) The cured state of each sample was evaluated over time.
Judgment Criteria XX: Start of reaction Aggregate (crystal) formation XX: Sample adheres when touched with finger X: Sample does not adhere when touched with finger, but finger mark remains △: Powdery when scratched with nail Scrapes into pieces and collapses when pressure is applied. ▲: Finger marks do not remain even when pressed with a finger. ○: No marks are left even when scratched with nails.
Also, it does not disintegrate even if pressure is applied. 〇 〇: Does not dissolve even if water is dropped Note 1: The concentration value indicates the concentration of the substance in the aqueous solution Note 2: The concentration is 5 wt%, and it is alkaline Exhibits a pH of 9

* From the results shown in Table 4 above, sodium silicate, sodium carbonate, and potassium carbonate of the examples can be used as a curing agent (hydraulic reaction inducer) in terms of reaction rate and curing time as a two-component reaction curing type paint. is there.
In addition, with respect to the ammonia and sodium citrate of Comparative Examples 1 and 2, the curing time is long and a sufficiently cured coating film cannot be obtained.
Further, with the sodium hydroxide and potassium hydroxide of Comparative Examples 3, 4, and 5 and ordinary Portland cement, the hydraulic reaction starts in a short time and aggregate particles are generated by the hydraulic reaction.
The reaction behavior of sodium hydroxide and potassium hydroxide shows the same behavior as the hydraulic reaction when water is added to ordinary Portland cement.
From the above, it is judged that sodium silicate, sodium carbonate, and potassium carbonate are most suitable as the two-component type hydraulic reactive inorganic coating curing agent (hydraulic reaction inducer) of the present invention.

4) Substances that do not ionize calcium Sodium silicate, sodium carbonate and potassium carbonate selected from the above results are desirable substances because they are not calcium salts.
In particular, as shown in FIG. 1, silicates such as sodium silicate are polyvalent metal ions (calcium ions) as anions such as orthosilicate ion (SiO ₄ ⁴ ) and pyrosilicate ion (Si ₂ O ₇ ⁶ ) in an aqueous solution. , Iron ions, aluminum ions, etc.) to form a gel structure, and the property is used to suppress the crystallization of calcium ions eluted from concrete, and with the calcium ions inside concrete. An efflorescence inhibitor, a reinforcing material for deteriorated concrete, etc. containing silicate as a main component, which utilizes the effect of reacting and reinforcing the surface, has already been marketed.
In the present invention, for the purpose of imparting the above-mentioned properties of the silicate to the coating film and suppressing calcium ions eluted from calcium oxide contained in the main component of the main component, alumina cement, the aqueous solution of the alumina cement suspension of the present invention is used. It is judged that the substance is useful as a hydraulic reaction inducer (hardening agent) of the suspension.

5) Adjustment of hydraulic reaction inducer (curing agent) (painting)
Examples and comparative examples are shown below.

Note 1 Wako Pure Chemical Industries, Ltd. Reagent Hydraulic reaction inducer Efflorescence inhibitor Water retention effect Note 2 Wako Pure Chemical Industries Reagent Hydraulic reaction inducer JIS≡K1408-1966 Sodium silicate (sodium silicate) No. 1 Efro Antisense agent Water retention effect Note 3 Reagent manufactured by Wako Pure Chemical Industries, Ltd.Humidity reaction inducer Note 4 Reagent manufactured by Wako Pure Chemical Industries, Ltd.Hydrochemical reaction inducer Note 5 Wako Pure Chemical Industries, Ltd. Kojunyaku Kogyo Co., Ltd.Reagent Hydraulic reaction inducer Note 7 AKZO NOBEL Co., Ltd. Fibrin derivative Thickening effect Water retention effect Viscoelasticity modifier that imparts thixotropic viscosity
*8 Toagosei Co., Ltd. Thickener Sodium polyacrylate Viscosity control Highly viscous viscoelasticity modifier that imparts Newtonian viscosity.
Note 9 Thickening agent manufactured by San Nopco Co., Ltd. Urethane-modified polyether Newtonian High-viscosity viscoelasticity modifier that imparts viscosity
*10 San Nopco Mineral Oil Defoamer
*11 Henkel Technologies Japan Inc. acrylic resin emulsion NV=51% MFT=0°C
*12 BASF Japan Ltd. 1-liquid room temperature crosslinkable acrylic styrene resin emulsion NV=48% MFT=6°C
Note 13 BYK Silicone surfactant Polyether-modified siloxane Surface tension adjuster Wetting and leveling improvement *14 BYK Wetting dispersant High molecular weight block copolymer solution with pigment affinity group Surface force adjuster Wetting And leveling property improvement *15 Nippon Emulsifier Co., Ltd. Membrane forming aid (ethylene glycol mono 2-ethylhexyl ether) Membrane forming aid Adjusting the minimum film forming temperature (MFT) of resin

The compositions of Tables 5 and 6 described above were manufactured by the following procedure, and it was evaluated whether or not the properties as a curing agent of the two-component reaction curable coating material were achieved.
(1) Water and an alkali-providing substance were mixed using a tabletop disper and stirred until the alkali-providing substance was completely dissolved.
(2) Add a defoaming agent and a surface tension adjusting agent while continuing stirring.
(3) Add resin emulsion while continuing stirring.
(4) The film forming aid was gradually added while continuing stirring so that the resin emulsion did not cause a solvent shock.
(5) The thickener was added while continuing stirring.

The product obtained by the above procedure was aged for 18 hours to obtain a sample until the effect of the film-forming aid was obtained.

Judgment criteria State during manufacturing...
◯: Fluid liquid or viscous liquid without aggregates Δ: Aggregation occurred
×: Gel with no fluid Note 1: Remarkable heat generation State immediately after production...
◯: Fluid liquid or viscous liquid without aggregation △: Aggregation occurred
X: Gel state without fluidity, one week after production...
◯: Flowable liquid or viscous liquid without aggregation Δ: Separation is observed, but uniform liquid is obtained with stirring ▲: Aggregates exist even if stirred ×: Not liquid even with stirring Note 2: Put in a container that can be sealed and leave it indoors for 1 week

* From the above results, it is judged that Examples 6 to 17 can be used as a curing agent for a two-component reaction curing type coating material.
On the other hand, Comparative Examples 6 to 11 did not lead to the formation of aggregates or gels in 6 and 7, but the heat generation during stirring was observed, so that they were manufactured before being made into a paint (liquefying with fluidity). The problem turned out.
For Nos. 8 to 11, the dispersion (emulsion) of the resin particles tended to be unstable and aggregated, and it could not be made into a paint (liquefied with fluidity).

<Preparation of the main component containing alumina cement aqueous suspension as the main component (painting)>
The preparation (under paint) of the main component of the alumina cement-based two-component coating material, whose main component is alumina cement, using water-dispersible alumina cement (EXALT 60H) manufactured by KERNEOS is described below.
The following is an example of a composition optimized as a main component of an alumina cement-based two-component coating material (two-component reaction curing type coating material).

-Paint Liquid Properties A paint was prepared with the paint formulations shown in Tables 9 to 12, and the paint liquid properties immediately after the production and the storage stability after standing for 0 to 30 days in the room were confirmed.
Evaluation criteria Criteria Liquid properties...
◯: A uniform liquid with no aggregates and viscous ^(Note) Δ: A uniform liquid without aggregates, but not viscous ^(Note) ×: Shows liquid but poor fluidity ^Note that there is no viscous property ^(Note) The viscous property here is a viscous fluid liquid having Newtonian properties and thixotropic properties, and is different from a dilatancy viscous slurry liquid.
Storage stability...
◯ ◯: A uniform liquid without agglomerates, which has fluidity ◯: A uniform liquid without agglomerates, which tends to thicken, but becomes a viscous liquid with agitation Δ: Aggregates No uniform liquid, high viscosity, poor fluidity even with stirring ×: Aggregate generated, high viscosity, no fluidity even with stirring, or viscous with aggregation Incompatible liquid
*1 KERNEOS (France) EXALT 60H Alumina cement aqueous suspension *2 Ishihara Sangyo Co., Ltd. powder titanium oxide color pigment *3 Yokohama Chemical Co., Ltd. dispersion titanium oxide coloring pigment *4 Silica fine aggregate body pigment * 5 DC latent hydraulic fine aggregate Blast furnace slag extender pigment *6 Calcium carbonate fine aggregate extender pigment *7 Showa KDE Co., Ltd. sepiolite (hydrated magnesium silicate) Coating reinforcer using water retaining fiber *8 Manufacturer: ENGELHARD Attapulgai stone Thickening effect Water retention effect Thixotropic viscosity Reinforcement using needle crystals Note 9 BYK wet dispersant Surface tension adjustment Wetability improvement Leveling property improvement Dispersibility improvement Color separation prevention Note 10 BYK silicon Surfactant Surface tension adjustment Wetting property improvement Leveling property improvement Dispersibility improvement Color separation prevention Note 11 Kao Corporation JIS A 6204 High performance water reducing agent (1 type)
Note 12 AKZO NOBEL non-ionic cellulose ether fibrin derivative Thickening effect Water retention effect Thixotropic viscosity Note 13 Toagosei Co., Ltd. thickener Sodium polyacrylate viscosity control Newtonian viscosity Note 14 San Nopco thickener Urethane-modified polyether Newtonian high-viscosity viscoelasticity modifier *15 San Nopco Ltd. mineral oil defoamer *16 San Nopco Ltd. nonionic powder type defoamer *17 Osaka Gas Chemicals Organic nitrogen sulfur compound Antibacterial agent Note 18 Silicon compound Hydrophobicity agent Anti-rust effect Note 19 BASF Japan 1-liquid room temperature crosslinkable acrylic styrene resin emulsion NV=48%
FT=6℃ Aid for film formation Water retention in the initial stage Prevention of dry cracking Note 20 Henkel Technologies Japan Acrylic resin emulsion NV=51%
MFT=0°C Aid for film formation Water retention in early stage Prevention of dry cracking Note 21 Asahi Glass Co., Ltd. Fluororesin emulsion NV=51% MFT=30°C
Water-retention in the early stages of film formation Prevention of water cracking *22 Wako Pure Chemical Industries, Ltd. reagent sterilizing action Antiseptic effect Delayed hydraulic reaction Note 23 Wako Pure Chemical Industries, Ltd. reagent Hydraulic reaction inducer Reduction action Antiseptic effect Antirust effect Water Delay of hard reaction Note 24 Nippon Emulsifier Co., Ltd. Film-forming aid (plasticizer) Adjusting the minimum film-forming temperature (MFT) of resin Evaporation control of water

*1 KERNEOS (France) EXALT 60H Alumina cement aqueous suspension *2 Ishihara Sangyo Co., Ltd. powder titanium oxide color pigment *3 Yokohama Chemical Co., Ltd. dispersion titanium oxide coloring pigment *4 Silica fine aggregate body pigment * 5 Latent hydraulic fine aggregate made by DC Co., Ltd. Blast furnace slag body pigment *6 Calcium carbonate fine aggregate body pigment *7 Showa KDE Co., Ltd. sepiolite (hydrated magnesium silicate) 8 Manufacturer: ENGELHARD Attapulgai stone Thickening effect, water retention effect, thixotropic viscosity Note 9 BYK wet dispersant Surface tension adjustment Wetting improvement Improving leveling property Dispersion improvement Color separation prevention Note 10 BYK silicone surfactant surface Tension adjustment Wettability improvement Leveling property improvement Dispersibility improvement Color separation prevention Note 11 Kao Corporation JIS A 6204 High performance water reducing agent (1 type)
Note 12 AKZO NOBEL non-ionic cellulose ether fibrin derivative Thickening effect Water retention effect Thixotropic viscosity Note 13 Toagosei Co., Ltd. thickener Sodium polyacrylate viscosity control Newtonian viscosity Note 14 San Nopco thickener Urethane-modified polyether Newtonian high-viscosity viscoelasticity modifier *15 San Nopco Ltd. mineral oil defoamer *16 San Nopco Ltd. nonionic powder type defoamer *17 Osaka Gas Chemicals Organic Nitrogen Sulfur Compound Antibacterial Agent
Note 18 Silicone compound Hydrophobicity imparting agent Anti-rust effect imparting Note 19 BASF Japan Ltd. 1 liquid room temperature crosslinkable acrylic styrene resin emulsion NV=48% MFT=6°C
Membrane Assistance Initial Water Retention Water Dry Crack Prevention Note 20 Henkel Technologies Japan Acrylic Resin Emulsion NV=51%
MFT=0℃
Membrane formation assistance Water retention in the early stage Prevention of dry cracking Note 21 Asahi Glass Co., Ltd. Fluororesin emulsion NV=51% MFT=30℃
Water-retention in the early stages of film formation Prevention of dry cracking*22 Wako Pure Chemical Industries, Ltd. reagent sterilizing action Antiseptic effect Delayed hydraulic reaction Note 23 Wako Pure Chemical Industries reagent Reactant Hydrophilic reaction inducing substance Reduction action Antiseptic effect Rust prevention effect Water Hard reaction delay Note 24 Nippon Emulsifier Co., Ltd. Film-forming aid (plasticizer) Adjusting the minimum film-forming temperature (MFT) of resin Evaporation control of water

*1 KERNEOS (France) EXALT 60H alumina cement aqueous suspension *2 Ishihara Sangyo Co., Ltd. powder titanium oxide color pigment *3 Silica fine aggregate body pigment *4 DC Co., Ltd. blast furnace slag body pigment latent hydraulic Fine aggregate A (specific surface area = 10,000 cm ² /g or more, dispersion pH = 12 to 13)
DC Co., Ltd. Blast furnace slag extender pigment latent hydraulic fine aggregate B (specific surface area = 3500 cm ² /g or more to less than 5000 cm ² /g dispersion liquid pH = 9 to 10)
Note 5 Calcium carbonate Fine aggregate extender Note 6 Showa KDE Co., Ltd. sepiolite (hydrated magnesium silicate) Coating reinforcer using water retention and fibrous material Note 7 Manufacturer: ENGELHARD Attapulgai stone Thickening effect, water retention effect Thixotropic Viscosity Note 8 Nippon Paper Industries Co., Ltd. Cellulose powder Water-retaining and fiber-reinforced coating agent Average fiber length = 45≡
Note 9 Cellulose powder manufactured by Nippon Paper Industries Co., Ltd. Membrane reinforcing agent using water retention and fiber average fiber length = 24≡
*10 BYK wet dispersant surface tension adjustment wettability improvement leveling property improvement dispersibility improvement color separation prevention *11 BYK silicon surfactant surface tension adjustment wettability improvement leveling property improvement dispersibility improvement color separation prevention *12 Kao Corporation JIS A 6204 High-performance water reducing agent (1 type)
Note 13 AKZO NOBEL non-ionic cellulose ether fibrin derivative Thickening effect Water retention effect Thixotropic viscosity Note 14 Toagosei Co., Ltd. thickener Sodium polyacrylate viscosity control Newtonian viscosity Note 15 San Nopco thickener Urethane-modified polyether Newtonian high-viscosity type viscoelasticity modifier *16 Sannopco Ltd. mineral oil defoamer *17 Sannopco non-ionic powder type defoamer *18 Osaka Gas Chemicals Organic Nitrogen Sulfur Compound Antibacterial Agent
Note 19 BASF Japan's silicon compound Hydrophobicity imparting agent Anti-rust effect added Note 20 Henkel Technologies Japan's acrylic resin emulsion NV=51% MFT=0°C
Membrane formation assistance Water retention in the initial stage Prevention of dry cracking Note 21 Wako Pure Chemical Industries, Ltd. reagent Sterilizing action Antiseptic effect Delayed hydraulic reaction Solubility in water = 5.6g/100mL (20℃)
*22 Wako Pure Chemical Industries, Ltd. Reagent Hydraulic reaction inducer Reduction action Antiseptic effect Anticorrosion effect Delayed hydraulic reaction Solubility in water = 5.9g/100mL (20℃)

*1 KERNEOS (France) EXALT 60H Alumina cement aqueous suspension *2 Ishihara Sangyo Co., Ltd. powder titanium oxide color pigment *3 Yokohama Chemical Co., Ltd. dispersion titanium oxide coloring pigment *4 Silica fine aggregate body pigment * 5 Latent hydraulic fine aggregate made by DC Co., Ltd. Blast furnace slag extender Note 6 Calcium carbonate fine aggregate extender Note 7 Showa KDE Co., Ltd. Sepiolite (hydrated magnesium silicate) Water-retaining and fiber-reinforced coating Note 8 Manufacturer: ENGELHARD Attapulgai stone Thickening effect, water retention effect, thixotropic viscosity Reinforcement using needle-like crystals Note 9 BYK wet dispersant Surface tension adjustment Wetability improvement Leveling property improvement Dispersion improvement Color separation prevention Note 10 BYK Silicone surfactant, surface tension adjustment, wettability improvement, leveling property improvement, dispersibility improvement, color separation prevention Note 11 Kao Corporation JIS A 6204 High-performance water reducing agent (1 type)
Note 12 AKZO NOBEL non-ionic cellulose ether fibrin derivative Thickening effect Water retention effect Thixotropic viscosity Note 13 Toagosei Co., Ltd. thickener Sodium polyacrylate viscosity control Newtonian viscosity Note 14 San Nopco thickener Urethane-modified polyether Newtonian high-viscosity viscoelasticity modifier *15 San Nopco Ltd. mineral oil defoamer *16 San Nopco Ltd. nonionic powder type defoamer *17 Osaka Gas Chemicals Organic nitrogen sulfur compound Antibacterial agent Note 18 Silicon compound Hydrophobicity imparting agent Anti-rust effect Note 19 BASF Japan 1-liquid room temperature crosslinkable acrylic styrene resin emulsion NV=48% MFT=6°C
Membrane formation assistance Water retention in the initial stage Prevention of dry cracking Note 20 Henkel Technologies Japan Acrylic resin emulsion
NV = 51% MFT = 0°C
Membrane formation assistance Water retention in the early stage Prevention of dry cracking
*21 Asahi Glass Co., Ltd. Fluororesin emulsion NV=51% MFT=30℃
Membrane formation assistance Water retention in the early stage Prevention of dry cracking
Note 22 Wako Pure Chemical Industries, Ltd. Reagent: germicidal action, antiseptic effect, delayed hydraulic reaction Note 23: Wako Pure Chemical Industries, Ltd. reagent, hydraulic reaction-inducing substance, reducing action, antiseptic effect, antirust effect, delayed hydraulic reaction Note 24: Nippon Emulsifier Co., Ltd. Film-forming aid (plasticizer) Adjusting the minimum film-forming temperature (MFT) of resin Suppressing water evaporation

* From the above, in order to obtain the coating liquid properties as the main component of the alumina cement-based two-component paint (two-component reaction curing type paint), simply use water-dispersed alumina cement (EXALT 60H) as in Comparative Examples 13 and 14. The addition of a coloring agent to is not suitable as a coating liquid property because of high dilatancy viscosity.
By adding a thickener containing a surfactant or a viscosity control agent as in the compositions of Examples 18 to 51, and further a resin emulsion or the like, a viscous material that exhibits a Newtonian property and a thixotropic property in accordance with the shear rate. It becomes a liquid and has the best coating properties.
The coating liquid is a liquid having the above-mentioned viscous Newtonian property and thixotropic property in order to prevent sagging when applied to a vertical wall, smoothness of the finished surface, and further exhibit good coating workability. It is an important factor.

When the latent hydraulic fine aggregate (blast furnace slag) is added to the extender pigment, the storage stability is improved by using boric acid or tetrasodium pyrophosphate as a blocking agent alone or in combination.
The deterioration of storage stability is not caused by the alkalinity of the water-dispersible alumina cement (EXALT 60H), which is alkaline and induces a hydraulic reaction, due to the alkalinity of the latent hydraulic fine aggregate (blast furnace slag, pH 9-12 of the aqueous dispersion). Because it becomes stable, boric acid (solubility in water 5-6g/100ml.20°C) which is a blocking agent for water-dispersible alumina cement (EXALT 60H) or tetrasodium pyrophosphate (phosphorus compound) (solubility in water 5 ~6g/100mL.20°C) can be solved by adding an amount that gives a supersaturated concentration. (Examples 46 to 51)
Storage stability cannot be maintained with no addition of a blocking agent or with an addition amount of a concentration that does not reach a supersaturated state. (Comparative Examples 18 to 23)
Create examples of the following items:

<Mixed liquid properties of main agent and curing agent>
1) Pot life (pot life)
The pot life (working time) of the coating liquid (mixture of the main agent and the curing agent), which is a combination of the above-mentioned hydraulic reaction inducer (hardener) example and the main agent example of the alumina cement aqueous suspension, is confirmed. ..
The confirmation method is as follows (1) Test method
Conforms to JIS K5600-2-6: 1999 "General paint test methods-Part 2: Properties and stability of paints-Section 6: Pot life" (2) Acceptance criteria
Compliant with JIS K5659-7-7: 2008 "Weather resistant paint for steel structures, pot life"
(3) According to the JIS standard, the pot life (pot life) is evaluated at 5 hours, but in this case, the evaluation was also carried out at 8 hours and 24 hours in consideration of the usage time at the actual work.




*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersion Improvement Color Separation *3 Sannopco Mineral Oil Defoaming agent Note 4 DC Co. latent hydraulic fine aggregate blast furnace slag extender pigment A: specific surface area = 10000 cm ² / g or more B: specific surface area = 3500 cm ² / g or more ~5000cm ² / g under Note 5 manufactured by Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction
*1 KERNEOS (France) manufactured by TANAL WHITE (powdered alumina cement)
Note 2 Within 3 hours, solidified (solid) state

* From the above examples, the main agent composition mainly composed of the alumina cement aqueous suspension and the hardener composition mainly composed of the alkaline hydraulic reaction inducer sodium carbonate, potassium carbonate, and sodium silicate proposed in the present invention. It has been confirmed that the combination of the main agent and the curing agent of the product has a sufficient pot life (pot life) as a two-component room temperature reaction curing type coating material.
On the other hand, in the case of the curing agent composition containing sodium hydroxide or potassium hydroxide as the main component as the alkaline hydraulic reaction inducer of the comparative example, the pot life (pot life) was JIS K5659-7-7:2008 Weatherproof paint for pots" is not applicable and cannot be used in actual painting work.
Furthermore, the ordinary dispersion of Portland cement or the dispersion of alumina cement undergoes an apparent curing (solidifying) reaction before the pot life (pot life) required for a two-component room temperature reaction-curing paint. Resulting in.
In the above examples, it was revealed that the pot life (pot life) was remarkably extended in the combination with the curing agent composition containing sodium silicate as the main component which is the alkaline hydraulic reaction inducer. It represents the characteristics of the invention, and in the following sections, it is proposed to make a paint with two components as a paint form, in the title of "alumina cement-based two-component paint" in the present invention. It is also possible to explain.
Therefore, the present invention is not limited to the two-component type coating (two-component room temperature reaction curing type coating), and one-component type coating (one-component room temperature reaction curing type (self-crosslinking type or self-curing type) coating) It also includes.

2) Evaluation procedure
(1) Storage stability The sample prepared above is put in a hermetically sealed container and stored in a room (temperature 23 ± 2°C and relative humidity 50 ± 5%) for 1, 2 or 3 months, and the appearance of the sample solution is observed. ..
(2) Coating workability The coating workability of the brush, roller, and air spray was confirmed for the sample liquids with storage periods of 1, 2 and 3 months.
(3) Confirmation of hydraulic reaction of alumina cement as hydraulic binder
Sample liquids with a storage period of 1, 2 or 3 months were applied to the slate plate by air spray and cured for 7 days indoors (temperature 23±2℃ and relative humidity 50±5%) as test specimens. Conduct boiling test for 1 week.
Further, the adhesion after the boiling test was carried out in accordance with JIS K5600-5-6: 1999 General test method for paint-Part 5: Mechanical properties of coating film-Section 6: Adhesion (cross-cut method) ..
(The number of grids is 25 and the grid spacing is 4 mm. The tape used is a non-standard packing tape with high adhesive strength.)
As a comparative example, a slate plate coated with mortar using ordinary Portland cement, a plate coated with mortar using alumina cement, and an acrylic urethane resin emulsion-based paint from another manufacturer were painted according to the manufacturer's recommended coating specifications. The test was carried out by adding the plate to which the boiling was applied in each boiling test.
Note: As long as the hydraulic reaction of cement is sufficiently advanced, no abnormality will occur even when immersed in boiling water, but in the case of a coating formed by resin, abnormal appearance such as swelling or peeling will occur at an early stage. A boiling test was carried out to confirm the hydraulic reaction of alumina cement from the past knowledge that the occurrence of the phenomenon.
*1 Use an air sprayer with a diameter of 1.5 mm. *2 Classification evaluation conforms to JIS K5600-5-6-8-3 Table 1.

*1 Use an air sprayer with a diameter of 1.5 mm. *2 Classification evaluation conforms to JIS K5600-5-6-8-3 Table 1.

*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersibility Improvement Color Separation *3 Sannopco Mineral Oil Defoaming agent Note 4 DC Co. latent hydraulic fine aggregate blast furnace slag extender pigment A: specific surface area = 10000 cm ² / g or more B: specific surface area = 3500 cm ² / g or more ~5000cm ² / g under Note 5 manufactured by Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction Note 6 KERNEOS (France) Note 7 Commercial item Note 8 Air spray with a diameter of 1.5 mm Note 9 Classification evaluation is JIS K5600-5-6-8- Conforms to Table 1 of 3 Note 10 Nippon Paint Co., Ltd. Undercoat: Nippe Perfect Filler
Topcoat: Audeflesh U1002 The coating method conforms to the manufacturer's coating specifications.

* In the above example, a mixed liquid of a main agent composition containing an alumina cement aqueous suspension containing a hydraulic binder as a main component and an alkaline curing agent composition containing sodium silicate as a main component to induce a hydraulic reaction. Even after 4 months, there was no problem in coating and there was no abnormality when immersed in boiling water.
This means that the hydraulic property of the alumina cement did not disappear for 4 months, and further, the effect of inducing the hydraulic reaction of the main component containing sodium silicate as a main component worked, and the coating film obtained thereby Unlike the organic coating film containing resin as a main component, a coating film having properties similar to those of the cement-based solidified product was formed as compared with the comparative example.
From the above, in the present invention, a coating composition obtained by mixing a main agent composition containing an alumina cement aqueous suspension containing a hydraulic binder as a main component and an alkaline curing agent composition containing sodium silicate as a main component to induce a hydraulic reaction. The liquid can be made into one component, and can be a one-component type coating (one-component normal temperature reaction curing type (self-crosslinking type or self-curing type) coating) in the coating market.
Regarding the present invention, the two-component type coating was claimed in the above Examples, etc., but by limiting the alkaline curing agent composition that induces the hydraulic reaction to sodium silicate, the work in the field is simple and the main agent and the curing agent are It was found that a one-component coating material that can prevent compounding mistakes (forgetting to add a curing agent) can be realized.

<Special coating performance>
1) Adhesion to wet surfaces In the "Construction standard specifications/commentary JASS18 painting work", the water content of the painting base is strictly limited, and construction on wet base is not allowed.
However, since the coating material of the present invention contains alumina cement, which is a hydraulic reaction component, as a main component, it is possible to sufficiently secure the adhesiveness to the base material in a wet state.
The mixed solution of the main agent and the curing agent described in the above Tables 13 to 16 was used as a sample, and the mortar compounded with ordinary Portland cement/7 silica sand/water=1 part/3 parts/0.5 part was coated in a wet state, and the next day. And the adhesiveness after 7 days was confirmed.
(1) Evaluation procedure Knead mortar in the above ratio, pour it into a mold with a depth of 20 mm, and leave it in a room (temperature 23 ± 2°C and relative humidity 50 ± 5%) for 3 hours.
After confirming the solidification by touching with a finger, apply the samples of Tables 13 to 16 with a brush at an amount of 400 g/m ² /2 times, and check the adhesion on the next day and 7 days after JIS K5600-5-6: 1999 General paint test. Method ≡ Part 5: Mechanical properties of coating film ≡ Section 6: Adherence (cross-cut method).
Furthermore, observe the appearance of the coating film after 7 days.
Note 1 In addition to confirmation by touching with a finger, an error display of more than 15% was confirmed with a concrete mortar moisture meter HI-520-2 (measurement range: mortar: 0 to 15%) manufactured by Kett Scientific Research Co., Ltd.
Normally, with organic resin paints, when painting on concrete or mortar base, the water content of the base is set to 10% or less in the "Construction Standard Specification/Commentary JASS18 Painting Work".
Note 2 The tape used was a packing cloth tape with a strong adhesive strength that is out of this standard. (The number of grids is 25 and the grid spacing is 4 mm.)

(2) Criteria
・ Visually check the appearance of the coating for abnormalities such as gloss, color tone, and wrinkles. ◯: No abnormality ×: Loss, change in color tone, unevenness, wrinkles, etc.
・Adhesiveness
JIS K5600-5-6: 1999 General test method for paint ≡ Part 5: Mechanical properties of coating film ≡ Section 6: Adhesion (cross-cut method) according to the classification listed in Table 1 of 8-3 ..
As a comparative example, an acrylic urethane resin emulsion-based paint injection from another company was added.
Note) Undercoat made by Nippon Paint Co., Ltd.: Nippe Perfect Filler Topcoat: Audeflesh U1002
Painting method conforms to the manufacturer's painting specifications




*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersibility Improvement Color Separation *3 Sannopco Mineral Oil Defoaming Agent Note 4 Latent hydraulic micro-aggregate blast furnace slag extender pigment A: Specific surface area = 10,000 cm ² /g or more B: Specific surface area = 3500 cm ² /g or more to less than 5000 cm ² /g Note 5 Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction

* From the above, the coating material of the present invention has a high water content of the coating base, and even if it is coated in a wet state, sufficient adhesion is exhibited, and there is obtained a result that there is no abnormality in designability.
This is a problem that existing organic resin-based paints have, specifically painting civil engineering structures (retaining walls, bridge girders, tunnel walls, etc.) that always maintain a high water content, and also water absorption. The coating material of the present invention is a finishing material that can solve the current situation that coating on a lightweight precast concrete plate containing a large amount of artificial aggregate (lightweight aggregate) of high quality is almost avoided because swelling or peeling occurs.

2) Construction compatibility with aluminum-based materials In general, materials containing mainly Portland cement as a main component have strong alkalinity, and therefore have a corrosive effect on aluminum (including surface-treated aluminum) materials. , Not constructed.
Also, the sulfuric acid anodized film used on aluminum sashes used in windows and doors does not have sufficient adhesion for paints whose main component is organic resin, so avoid it when painting at repair sites. Has been.
The evaluation of corrosiveness and adhesion to aluminum will be described below in Examples.
The mixture liquid of the main agent and the curing agent listed in Tables 13 to 16 above is applied to an aluminum plate as a sample to make a test body, and the adhesion is evaluated by JIS K5600-5-6: 1999 General test method for paint-Part 5 : Mechanical properties of coating film-Section 6: Corrosion to aluminum based on adhesion (cross-cut method) is observed immediately after application of the sample and a test piece immersed in tap water for 1 month. The evaluation was performed by the change in appearance.
Note The tape used is a non-standard strong adhesive tape for packing. (1) Evaluation procedure Alloy A6063 (Al-Mg-Si alloy) used in aluminum sashes and anodized film Using the material (Note 1) coated with a sulfuric acid film (silver) as the base material, apply the mixed solution of the main agent and the curing agent listed in Tables 13 to 16 in an amount of 400 g/m ² /2 times, and then for 7 days. A specimen that was aged in a room at a temperature of 23 ± 2°C and a relative humidity of 50 ± 5% was used as a test sample.
As a comparative example, ordinary Portland cement/7 silica sand/water = 1 part/3 parts/0.5 parts mortar mixed onto the above-mentioned base material with a wet film thickness of 1.5 mm, and a solvent-based two-liquid room temperature. An evaluation was carried out by adding a reaction-curable fluororesin paint and an oil-based paint (Note 2) applied to the above-mentioned base material according to the manufacturer's standard specifications.
In the water immersion test, the side surface and back surface of the test piece were exposed with the base material exposed.
Note 1 Sealed product
Note 2 Solvent-based 2-liquid room temperature reaction-curable fluororesin paint
AGC Co-Tech Co., Ltd. Fluorine resin paint finish for metal materials: Undercoat: Bon Epocoat #35HB Solvent-based 2 liquid room temperature reaction-curable epoxy resin paint Intermediate coating: Bonflon #2000HB Medium coat Solvent-based 2 liquid room temperature reaction curable urethane resin coating Topcoat: Bonflon GT#2000SR Topcoat Solvent-based 2-liquid room temperature reaction-curable fluororesin paint Oil-based paint Asahipen Corporation Silicon-modified alkyd resin paint
One-time coating finish Required amount = 0.1 l/m ²

(2) Judgment criteria-presence or absence of corrosiveness Visually observe the state immediately after application.
◯: No reaction even when the coating liquid contacts the substrate ×: When the coating liquid contacts the substrate, a reaction involving generation of gas occurs. After the water immersion test, visually inspect the exposed parts of the base material.
◯: No abnormality is recognized.
×: Abnormalities such as discoloration due to corrosion and traces of elution are observed ・Adhesiveness
JIS K5600-5-6: 1999 General test method for paint ≡ Part 5: Mechanical properties of coating film ≡ Section 6: Adhesion (crosscut method) according to the classification listed in Table 1 of 8-3 ..





*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting Dispersant Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersibility Improvement Color Separation *3 San Nopco Mineral Oil Defoaming agent Note 4 DC Co. latent hydraulic fine aggregate blast furnace slag extender pigment A: specific surface area = 10000 cm ² / g or more B: specific surface area = 3500 cm ² / g or more ~5000cm ² / g under Note 5 manufactured by Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction


Note Due to the stress when making a notch with a cutter knife, peeling from the substrate was not observed, and the adhesion is good.

* From the above, conventional cement-based finishing materials cannot be applied to aluminum-based materials due to the problem of corrosion, and conventional organic resin-based paints have poor adhesion to the anodized film. Compared to the aluminum-based materials that were avoided, the coating of the present invention does not corrode and there is no problem with the primary and secondary adhesion performance to the anodized film, so it seems that it can be adequately applied to construction. ..

3) Ultraviolet resistance Since conventional organic resin-based paints form a coating film by the binding force of the organic resin, which is a main component, the ultraviolet resistance depends on the resin contained and therefore has a limit.
On the other hand, since the coating composition of the present invention depends on the crystallization of the inorganic substance by the hydraulic reaction of the alumina cement for the coating film formation, the ultraviolet resistance is far higher than that of the organic resin coating composition.
As a familiar example, while the RC structure has been exposed to ultraviolet rays and has not collapsed for 50 to 100 years, the organic resin-based coating is a fluororesin coating excellent in ultraviolet resistance. Even if it exceeds 20 years, loss and choking, which is a decomposition phenomenon of resin, will appear.
For the above, a continuous irradiation promotion test of ultraviolet rays by a metal halide lamp was carried out.
Note that this test is different from accelerated weathering, and is an evaluation that is specialized only for deterioration due to ultraviolet energy.

(1) Evaluation procedure, model used and setting conditions Model: Metaling weather meter M6T Suga Test Instruments Co., Ltd. Wavelength: 300 to 400 nm (Note 1)
Emissivity: 2000W/m ²
Temperature: 63±3℃
Humidity: 50±5%RH
Irradiation time: 200 hours continuous Radiation exposure: 1441MJ/m2 (Note 2)

Note 1: Wavelength in the ultraviolet range emitted from the metal halide lamp
Note 2 Radiation exposure amount Radiation exposure amount of sunlight If the average annual radiation exposure amount of sunlight in Japan is 4500 MJ/m2 (*1), the emission of each wavelength of ultraviolet, visible, and infrared (*2) The exposure amount MJ/m2 is as shown in Table 31 below.

The relationship between the irradiance of the accelerated weather resistance test and the test time is as shown in Table 32 below.

Note 1 The degree of acceleration when considering only the amount of UV irradiation, which is based on the general sunshine carbon arc used in accelerated weathering tests.
Note 2 The sunshine carbon arc light source weather tester (SWOM) is a tester that uses the sunshine carbon arc light source.
When the test time according to the radiation exposure amount is calculated, this test is exposed to the ultraviolet rays corresponding to 5000 hours of the sunshine carbon arc (Sunshine carbon arc lamp type weather resistance tester (SWOM)).

-Preparation of test sample Example 64 and Example 92 were applied to two slate plates (size 150 x 50 x 4 mm) with an application amount of 400 g/m ² /2 times by air spraying, and the temperature was 23 ± 2°C and relative humidity. A specimen that was cured in a room of 50±5% for 14 days was used as a test body.
As comparative examples 29 and 32, the fluororesin emulsion type paint (Note) manufactured by AGC Co-Tech Co., Ltd. was applied according to the manufacturer's standard specifications, and the same curing as above was performed.
One of the two was tested, and the remaining one was stored as a comparison plate (sample plate) in the dark.
Note AGC Co-Tech's water-based fluororesin paint Base coat: Bonflon water-based primer S Required amount = 0.12-0.15kg/m ²
Intermediate coating: Bonflon water-based W#1500 Required amount = 0.13-0.16kg/m ²
Topcoat: Bonflon water-based W#1500 Required amount = 0.13-0.16kg/m ²
(2) Judgment Criteria By visual observation, evaluate whether there is a difference with the sample board (comparative board)


* From the above, it is clear that the coating composition of the present invention is resistant to ultraviolet rays and superior to organic resin coating compositions.
This is because in the construction field, as a reduction in life cycle cost, a finishing material that extends the cycle of repainting (repair work) is desired. It can be said that it is a paint that can greatly extend the cycle of once in 40 years and greatly reduce the life cycle cost.

4) Crack resistance by drying
(1) Crack resistance due to drying at room temperature and humidity (temperature 23 ± 2 ≡ °C, humidity 50 ± 5%) ・Evaluation procedure and evaluation criteria are JIS A 6909-7-8:2003 Crack resistance due to initial drying Same as the sex test. The test piece was applied to the slate plate with air spray at an application amount of 400 g/m ² /2 times.





*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersibility Improvement Color Separation *3 Sannopco Mineral Oil Defoaming Agent Note 4 Latent hydraulic micro-aggregate blast furnace slag extender pigment A: Specific surface area = 10,000 cm ² /g or more B: Specific surface area = 3500 cm ² /g or more to less than 5000 cm ² /g Note 5 Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction

(2) Resistance to cracking due to drying in hot weather in summer ・In August 2017, the result of painting on the retaining wall of our parking lot (1611 Shimokurokoma, Misaka-cho, Fuefuki-shi, Yamanashi Prefecture).
Retaining wall surface temperature: 37℃
Ambient temperature: 39-42℃
Coating method: Medium hair roller coating 2 times coating usage: 400-500g/m ²


(3) Crack resistance due to drying due to difference in coating amount-The evaluation procedure and evaluation criteria are in accordance with JIS A 6909-7-8:2003 Crack resistance test due to initial drying.
The test piece was a slate plate coated with air spray at a coating amount of 200 to 1000 g/m ² /2 to 5 times.
For comparison, a test was conducted by adding the top coat material (Note 1) of Comparative Example 29 and the top coat material (Note 2) of Comparative Example 32.
Note 1: Acrylic urethane resin emulsion paint by Nippon Paint Co., Ltd. Oude Fresh U1002
*2 AGC Co-Tech Co., Ltd. Fluororesin emulsion paint Bonflon water-based W#1500





*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersion Improvement Color Separation *3 Sannopco Mineral Oil Defoaming agent Note 4 DC Co. latent hydraulic fine aggregate blast furnace slag extender pigment A: specific surface area = 10000 cm ² / g or more B: specific surface area = 3500 cm ² / g or more ~5000cm ² / g under Note 5 manufactured by Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction


* From the above, the coating composition of the present invention does not cause a cracking phenomenon in the drying process, which is a weak point of cement which is a hydraulic reaction product, and satisfies the film forming property as a coating composition.
Furthermore, cracking due to surface drying in a thick film is less likely to occur than in conventional organic resin-based paints, and it can be said that thick film finishing is possible.

5) Development of hardness of coating film In general, an organic resin-based coating material for construction has plasticity and low hardness because the film-forming property is prioritized. It has high hardness because it depends on the reaction.

Below, using a mixed solution of the main agent and the curing agent described in Tables 13 to 16 as a sample, an application amount of 400 g/m ² /2 times was applied to a slate plate by air spraying, the temperature was 23±2° C., and the humidity was 23° C. The hardness after 24 hours and 7 days under a drying condition of 50±5% is determined according to "JIS. K. 5600-5-4: 1999. General test method for paint-Part 5: Mechanical properties of coating film-Section 4: The result of evaluation according to "Scratch hardness (pencil method)" is described.
For comparison, a test was conducted by adding the top coat material (Note 1) of Comparative Example 29 and the top coat material (Note 2) of Comparative Example 32.
Note 1: Acrylic urethane resin emulsion paint by Nippon Paint Co., Ltd. Oude Fresh U1002
*2 AGC Co-Tech Co., Ltd. Fluororesin emulsion paint Bonflon water-based W#1500





*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersion Improvement Color Separation *3 Sannopco Mineral Oil Defoaming agent Note 4 DC Co. latent hydraulic fine aggregate blast furnace slag extender pigment A: specific surface area = 10000 cm ² / g or more B: specific surface area = 3500 cm ² / g or more ~5000cm ² / g under Note 5 manufactured by Wako Pure Chemical Industries, Ltd. Reagents Bactericidal action Antiseptic effect Delayed hydraulic reaction


* From the above, the coating material of the present invention develops hardness rapidly, and can achieve coating film hardness that could not be found with conventional organic resin coating materials.
This can be said to be the result of the hydraulic reaction of the alumina cement contained in the paint functioning effectively.

6) Use as modifier of organic resin-based paint In the above-mentioned cases, in Example 97 of the paint of the present invention, a main agent composition containing an alumina cement aqueous suspension containing a hydraulic binder as a main component Since it has been found that it is possible to make a single agent in the state of mixing an alkaline curing agent composition that induces a hydraulic reaction mainly containing sodium silicate, the adhesion strength and coating film hardness of existing paints and emulsion resins. It can be considered to be applied to the use as a modifier.
Therefore, Example 97 was added to the emulsion resin to test the change in adhesion and the change in coating film hardness.
(1) Emulsion resin MFT and adjustment of foam breaking, defoaming and foam suppressing properties


*1 BASF Japan Ltd. 1-liquid room temperature crosslinkable acrylic styrene resin emulsion NV=48% MFT=7°C
*2 Henkel Technologies Japan Inc. acrylic resin emulsion NV=51% MFT=0°C
Note 3 Nippon Emulsifier Co., Ltd. plasticizer (ethylene glycol mono 2-ethylhexyl ether) Film forming aid Adjusting the minimum film forming temperature (MFT) of the resin Note 4 San Nopco Co., Ltd. mineral oil defoaming agent Defoaming and defoaming -Foam suppressing effect (2) Composition of Example 97

*1 KERNEOS (France) EXALT 60H Alumina Cement Aqueous Suspension *2 BYK Wetting and Dispersing Agent Surface Tension Adjustment Wetting Improvement Improving Leveling Improve Dispersion Improvement Color Separation *3 Sannopco Mineral Oil Defoaming Agent Defoaming/defoaming/foam suppressing effect *4 Wako Pure Chemical Industries, Ltd. Reagent Hydraulic reaction inducer Efflorescence inhibitor Water retention effect *5 Toagosei Co., Ltd. thickener Sodium polyacrylate Viscosity control Newtonian viscosity *6 BYK silicone surfactant Polyether-modified siloxane Surface tension adjusting agent Wetting and leveling improvement

(3) Adhesion and coating hardness A resin solution prepared by adjusting the MFT and the defoaming/foam-preventing property in 1) above was added with Example 97 of 2) above (mixture of main agent and curing agent). As a sample, a test body was prepared by applying a coating amount of 100 to 150 g/m ² /2 times to a slate plate by air spray. After drying in a room at a temperature of 23 ± 2°C and a humidity of 50 ± 5%, the coating film hardness after 24 hours and 7 days can be determined according to "JIS. K. 5600-5-4: 1999. General test method for paints-Part 5: Coating. Mechanical Properties of Membrane-Section 4: Scratch Hardness (Pencil Method)".
In addition, the adhesion after 7 days was measured according to "JIS K5600-5-6: 1999 General test method for paint ≡ Part 5: Mechanical properties of coating film ≡ Section 6: Adhesion (cross-cut method)". did.
However, the tape used was a cloth tape for packing, which has a non-standard adhesive strength.
The number of grids is 25 and the grid spacing is 4 mm.


* From the above, it is clear that the coating film hardness and the adhesive force are increased by adding the mixed liquid of the main component of the coating composition of the present invention and the curing agent to the resin liquid.
If this effect is utilized, strong adhesion and high coating hardness can be exhibited simply by adding it to the emulsion resin or the water-based paint.
Therefore, it can be used not only as a coating material but also as a modifier for a coating film.

According to the present invention, it is said that it is difficult to use the alumina cement-based two-component coating material, as well as the applications requiring strength, high level and acid resistance which are the merits of the conventional alumina cement-based two-component coating material. It can also be applied to various applications that require a thin film.
Specifically, the exterior of the structure is currently constructed with an organic resin-based paint whose main component is an organic resin that is easily affected by ultraviolet (UV) deterioration for the purpose of maintaining the beauty and protecting the structure. However, since it depends on the organic resin that is easily affected by ultraviolet (UV) deterioration, the effect of maintaining the beauty and protecting the structure is short, but by applying the alumina cement-based two-component paint of the present invention, the ultraviolet ( Since it is not affected by UV) deterioration, the cosmetics can be maintained and the structure can be protected for a long time.
Also, for materials with poor hardness and strength such as building materials and industrial products, the surface of the material can be modified to hardness and strength close to those of minerals and metals just by coating, so it can be used for surface treatment of materials. Is also available.
Further, the alumina cement-based two-component coating material of the present invention is not limited to what is called a coating material, and is also used as a modifier for improving hardness and strength of an organic resin or an organic resin-based coating material. be able to.

The alumina cement aqueous suspension used in the present invention may contain additional additives such as a water retention agent. These additives are preferably not only selected from water retention agents, surfactants , rheology agents and bactericides, but can also include plasticizers, antifoaming agents and thickeners.
The water retention agent includes an organic or inorganic fiber having a high water absorption property, a porous substance, an organic solvent having a function of suppressing evaporation of water, a resin, and the like.
The surfactant may have a function as a dispersant, a leveling agent, an antifoaming/foam suppressing agent, a wetting agent, and the like.
Further, as a dispersant suitable for use in the alumina cement aqueous suspension, there is Sokalan (registered trademark, manufactured by BASF Japan Ltd.) and the like, and the compounding ratio is 0.1% of the total weight of the alumina cement aqueous suspension. ˜3%, preferably 0.5 to 1%, or 0.1 to 5% by weight of the total weight of the hydraulic binder, preferably 0.6 to 1.8%.

The aqueous alumina cement suspension of the present invention may include fillers to form other compositions.
Such fillers can be selected from minerals or essentially organic and siliceous compounds, such as blast-furnace slags, carbonate compounds (calcium carbonate, dolomite), pigments, titanium oxide, light-reflecting substances such as perlite or vermiculite. There are fillers (sand, quartz, fumed silica).
As the pigment, firstly, a coloring pigment can be mentioned, and this coloring pigment also includes a functional pigment having performances such as high luster, light interference, heat shielding, and light storage.
Secondly, extender pigments are included, which also include fine aggregates and fine aggregates having latent hydraulic reactivity such as blast furnace slag.
And the filler is 10% to 30%, preferably 1 to 50% of the total weight of the composition, the remainder being formed from the aqueous alumina cement suspension.

Claims (7)

A stabilized alumina cement aqueous suspension containing the following alumina cement is used as a main component of the main component, and an alkaline liquid in which sodium silicate, sodium carbonate, or potassium carbonate dissolved to induce a hydraulic reaction of the suspension is dissolved in water. An alumina cement-based two-component coating material, characterized in that the main component and the hydraulic reaction inducer are separately packaged as a hard reaction inducer.
<Main ingredient of main agent>
A) Alumina cement suspension with a high content of alumina having an alumina content of 60% or more with respect to the total weight of the alumina cement aqueous suspension, 0.5% to 42% by weight.
B) Blocking agent containing phosphorus-containing compound in aqueous suspension of alumina cement 0.1% to 20% by weight
C) Blocking agent different from the phosphorus-containing compound in the aqueous suspension of alumina cement 0.3-5%, preferably 0.3-2.5%
D) Water-retaining agent (including organic solvent, resin, etc., which has a high water absorption property, organic or inorganic fiber or porous substance, and has an action of suppressing evaporation of water)
E) Surfactants (dispersing agents, leveling agents, defoaming/foam suppressing agents, wetting agents, etc.)
F) Viscosity modifier G) Coloring pigment (including functional pigments having performances such as high luster, light interference, heat shielding, and light storage)
H) extender pigment (including fine aggregate and fine aggregate with latent hydraulic reactivity such as blast furnace slag)
I) Antibacterial agent, antiseptic agent, antirust agent The blocking agent containing the phosphorus-containing compound is selected from any compound capable of forming any of these compounds by reacting with at least one metaphosphoric acid, phosphorous acid, phosphoric acid, phosphonic acid and water. Is a drug blocking containing a phosphorus-containing compound and boric acid and a borate compound,
The alumina cement-based two-component coating material according to claim 1, wherein the phosphorus-containing compound is contained in an amount of 0.1% by weight to 20% by weight based on the total weight of the alumina cement. The compound capable of forming metaphosphoric acid, phosphorous acid, phosphoric acid or phosphonic acid is phosphorus pentoxide, pyrophosphoric acid, tripolyphosphoric acid, aminotrimethylenephosphonic acid, 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, tetramethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, phosphonic acid pentamethylenediethylenetriamine, host recarboxylic acid, N-(phosphonomethyl)iminodiacetic acid, 2-carboxyethylphosphonic acid, Selected from 2-hydroxyphosphonocarboxylic acid,
The borate compound other than the phosphoric acid type is selected from sodium metaborate, sodium tetraborate and disodium trioxide octaboron tetrahydrate, and the alumina cement type 2 according to claim 2. Formulated paint. The alumina cement is an alumina high content alumina cement having an alumina content of 60% or more based on the total weight of the alumina cement aqueous suspension, and the relative weight of the phosphorus-containing compound is 0. The alumina cement-based two-component coating material according to any one of claims 1 to 3, which contains 5 to 42% by weight. The hydraulic reaction inducer for inducing a hydraulic reaction of the main agent is a substance having a high solubility in water containing sodium silicate, sodium carbonate and potassium carbonate and forming a highly alkaline aqueous solution. Alumina cement-based two-component paint according to any one of 4 above. The hydraulic reaction inducer for inducing the hydraulic reaction of the main agent is changed to a calcium salt compound or calcium hydroxide in which free calcium ions that cause precipitation of efflorescence are easily present when made into an aqueous solution. The alumina cement-based two-component coating material according to any one of claims 1 to 5, wherein no substance is used. A stabilized alumina cement aqueous suspension containing the following alumina cement is used as a main component of the main agent, and a hydraulic reaction inducer having sodium silicate as a main component is used. Alumina cement-based one-component paint characterized by being packaged in.
<Main ingredient of main agent>
A) Alumina cement suspension with a high content of alumina having an alumina content of 60% or more with respect to the total weight of the alumina cement aqueous suspension, 0.5% to 42% by weight.
B) Blocking agent containing phosphorus-containing compound in aqueous suspension of alumina cement 0.1% to 20% by weight
C) Blocking agent different from the phosphorus-containing compound in the aqueous suspension of alumina cement 0.3-5%, preferably 0.3-2.5%
D) Water-retaining agent (including organic solvent, resin, etc., which has a high water absorption property, organic or inorganic fiber or porous substance, and has an action of suppressing evaporation of water)
E) Surfactants (dispersing agents, leveling agents, defoaming/foam suppressing agents, wetting agents, etc.)
F) Viscosity modifier G) Coloring pigment (including functional pigments having performances such as high luster, light interference, heat shielding, and light storage)
H) extender pigment (including fine aggregate and fine aggregate with latent hydraulic reactivity such as blast furnace slag)
I) Antibacterial agent, antiseptic agent, antirust agent