JP2001302978A - Coating for reinforcing inorganic material and reinforced inorganic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating for reinforcing an inorganic material surely and easily capable of preventing generation of efflorescence without employing a special equipment such as an autoclave or the like and without necessitating complicated working processes and further without disturbing the inorganic material from hardening to prevent a hardened product thereof from exhibiting strength, and to provide a reinforced inorganic material. SOLUTION: The coating for reinforcing an inorganic material contains a complex-forming agent or a chelating agent bearing a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material so that the amount of the functional group contained is 10-4 to 5 mole equivalent based on 1 kg of the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic material reinforced paint and a reinforced inorganic material, and more particularly, to a method for suppressing the efflorescence phenomenon, strengthening the inorganic material itself, and coating the surface of the inorganic material. Enhance adhesion of coating film, etc.
Cement outer wall material, inorganic material reinforced paint and inorganic material reinforced paint that can contribute to strengthening of cement tiles and the like are applied,
Related to reinforced inorganic materials.

[0002]

2. Description of the Related Art In general, inorganic materials such as cement outer wall materials and cement roof tiles are known as substances that cause an efflorescence phenomenon. The efflorescence phenomenon refers to the movement of cations such as alkali metals and alkaline earth metals to the surface layer, reaction with carbon dioxide in the air, and the like, resulting in CaCO ₃ , Na ₂ SO ₄ , K ₂ SO ₄ , and Na ₂ CO 3. White squirts and spots (white blossoms) such as ₃ are deposited and bound on the surface, which means that the surface layer dissolves and chips or reduces the adhesion of the painted film. .

[0003] As a method of preventing efflorescence, for example, a method of promoting the reaction of unreacted alkali components by autoclaving to prevent florescence is generally performed. Autoclave curing is performed by treating at a high temperature and a high pressure for a certain period of time. Therefore, special equipment for carrying out the processing of a large number of products having complicated shapes is required, and the use of reinforcing fibers made of inorganic materials is restricted.

Further, the inorganic material is covered with an undercoating film made of an acrylic, urethane, vinyl chloride, or epoxy resin to reduce the water permeability to the inorganic material, and to reduce the alkali ion content in the inorganic material. A method of suppressing movement to the inorganic material surface layer is also generally performed. However, in order to surely lower the water permeability, for example, it is necessary to go through complicated steps such as undercoating, intermediate coating, topcoating and coating / drying, and to ensure adhesion of the coating film in each of these steps. It is a cumbersome method.

JP-A-5-170573 discloses a method for producing a cement molded plate in which an aqueous humate solution is applied or sprayed on a cured surface after primary curing and then secondary cured. However, in the method disclosed in the above publication, since cations such as alkali metals and alkaline earth metals in the cement molded plate are adsorbed and removed, the method inhibits the hardening of the cement molded plate. ,
There is a problem that the strength development of the cured product is affected.

[0006] Japanese Patent Application Laid-Open No. 8-208301 discloses that
A cation-adsorbing alkali-treated inorganic powder obtained by treating an inorganic material containing silica and alumina with an alkaline aqueous solution is mixed into ready-mixed concrete, and the added alkali-treated inorganic powder causes efflorescence on the concrete surface. A method is disclosed in which the generated alkaline ions are adsorbed to prevent the efflorescence of concrete.

However, in the method disclosed in the above publication,
Since the alkali-treated inorganic powder having a cation-adsorbing property is mixed in the concrete itself, it inhibits the hardening of the cement molding plate, and has a problem that the strength of the hardened body is affected.

Further, Japanese Patent Publication No. 7-53596 discloses that
As a countermeasure after the occurrence of efflorescence, a method is disclosed in which efflorescence generated on a hardened cement body is removed by washing with a chelating agent aqueous solution. Since this is a response after the occurrence of the eflorescence, some products may be relieved by this, but this does not prevent the occurrence of the eflorescence.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned facts, and has as its object the purpose of using an autoclave or other special equipment.
In addition, an inorganic material that can reliably and easily prevent the occurrence of efflorescence without requiring a complicated work process and without affecting the strength development of the cured product by inhibiting the curing of the inorganic material. It is to provide a reinforced paint and a reinforced inorganic material.

[0010]

According to a first aspect of the present invention, there is provided an inorganic material-reinforced coating material comprising a complex forming agent or a chelating agent having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material. , Binder resin 1k
The above functional group is contained in an amount of 10 ^{-4 to} 5 molar equivalents with respect to g.

According to a second aspect of the present invention, there is provided the inorganic material-reinforced coating composition, wherein a component having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material contains ^{10-4 to} 5 functional groups in the molecule. It contains a binder resin bound so as to have a molar equivalent / kg.

[0012] The inorganic material reinforced paint according to the third aspect of the present invention is the inorganic material reinforced paint according to the first or the second aspect, wherein the functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material is Hydroxyl, carbonyl, carboxyl, ether, ester, thiol, thioether, thioaldehyde, thioketone, thiocarbonyl, thiocarboxyl, thioamide, primary amine, secondary amine, tertiary Amine group,
Imine group, amide group, nitro group, nitroso group, N-oxide group, azo group, cyano group, sulfone group, phosphone group, phosphine group, primary-, secondary-, tertiary alkyl or allylphosphine group, phenyl group , An oxime group, a conjugated polyene group, a halogen (fluorine, chlorine, bromine, iodine) group and a Schiff base.

The reinforced inorganic material according to the fourth aspect of the present invention is obtained by applying the inorganic material reinforced paint according to the first, second or third aspect to the surface thereof.

In the present invention, the term "inorganic material" refers to an inorganic product or member produced by a manufacturing process involving a hydration reaction or the like, which may cause efflorescence.
Specifically, cement products such as tiles and outer wall materials can be mainly mentioned.

In the present invention, the complex-forming agent is a compound having a functional group capable of forming a complex with a cation eluted from the inorganic material, and the chelating agent is a compound forming a chelate compound with the cation eluted from the inorganic material. It is a compound having a functional group that can be performed, the functional group of the complexing agent or the chelating agent is not particularly limited as long as it has the above-described function, for example, nitrogen, oxygen, sulfur,
It contains an atom having an unshared electron pair such as silicon and phosphorus, or contains an atomic group having a π-conjugated electron such as a benzene ring or an unsaturated hydrocarbon, and specifically, a hydroxyl group, a carbonyl group, a carboxyl group , Ether group, ester group, thiol group, thioether group, thioaldehyde group, thioketone group, thiocarbonyl group, thiocarboxyl group, thioamide group, primary amine group, secondary amine group, tertiary amine group, imine group, amide Group, nitro group, nitroso group, N-oxide group, azo group, cyano group, sulfone group, phosphone group,
Examples include phosphine groups, primary-, secondary-, tertiary alkyl or allylphosphine groups, phenyl groups, oxime groups, conjugated polyene groups, halogen (fluorine, chlorine, bromine, iodine) groups, and Schiff bases.

As the chelating agent, specifically, ED
Ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), triethylenetetraminehexaacetic acid (TTHA), diethylenetriaminepentaacetic acid (DTPA), and trans-1,2-cyclohexanediamine, which are well-known as TA. Tetraacetic acid (CyDTA) and the like.

The binder resin used in the present invention is not particularly limited. For example, acrylic resins, urethane resins, olefin resins, halogenated olefin resins, epoxy resins, fluorine resins, Acrylic silicone resins and the like can be mentioned. Among them, fluorine resins, acrylic silicone resins and the like are preferably used because they can exhibit a higher degree of weather resistance of the obtained coating film.

When the content of the complex forming agent or the chelating agent with respect to the binder resin is less than 10 ^-4 molar equivalent per 1 kg of the binder resin, generation of efflorescence can be sufficiently suppressed. In contrast, if the molar ratio exceeds 5 molar equivalents, the adhesion of the coating film decreases, so that the above functional group is contained in an amount of 10 ^{-4 to} 5 molar equivalents.

As a means for introducing a functional group capable of forming a complex or a chelate compound with a cation eluted from an inorganic material into the binder resin, a method of mixing a complex-forming agent or a chelating agent with the binder resin described above is employed. Alternatively, a component having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material may be directly bonded to the binder resin molecule.

Means for directly bonding a component having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material in the binder resin molecule is not particularly limited. A method may be adopted in which a polymerizable compound having a functional group capable of forming a complex or a chelate compound with the eluted cation is polymerized or copolymerized with a compound copolymerizable therewith.

A polymerizable compound having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material is polymerized or copolymerized with the compound capable of forming a complex with the cation eluted from the inorganic material. When the binder resin obtained by the above method is used, it is preferable that the above-mentioned functional group is bonded to the binder resin molecule in an amount of 10 ^{−4 to} 5 mol equivalent / kg. However, even if there is an excess or deficiency of a component having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material in the binder resin molecule, a binder resin containing no component having such a functional group may be used. The desired amount or a substantial amount thereof can be contained by using a blend or a method of mixing the above-mentioned complex-forming agent or chelating agent in combination.

The inorganic material-reinforced coating material of the present invention may contain, if necessary, a dispersant, a dispersion stabilizer, a viscosity modifier, a thixo improver, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant,
Additives such as a coloring agent such as a pigment, a radical trapping agent, and a filler may be contained.

The form of the inorganic material-reinforced paint of the present invention is not particularly limited, and may be, for example, a one-pack type or a two-pack type. Further, it may be a solution type, an emulsion type using a dispersion medium such as water, or a powder type.

The means for applying the inorganic material reinforced paint of the present invention is not particularly limited, and examples thereof include a brush coating method, a roll coater method, a bar coater method, a curtain coater method, a transfer coating method, and a method of dipping. , Spraying, spraying, electrostatic coating and the like.

The inorganic material reinforced paint of the present invention is usually applied to the outermost layer of an inorganic material, but a protective layer consisting of a clear coating film may be further provided on the coating film.

The inorganic material-reinforced coating material of the present invention comprises a complex-forming agent or chelating agent having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material.
The above functional group is 10 ^{-4 to} 5 per kg of the binder resin.
Since it is contained so as to be a molar equivalent, at the time of molding the inorganic material, without using special equipment such as an autoclave, and without the need for complicated undercoating, work steps such as overcoating, Furthermore, it is possible to reliably and easily prevent the occurrence of efflorescence by simply coating the inorganic material without inhibiting the curing of the inorganic material and affecting the strength development of the cured product.

The inorganic material-reinforced coating material of the present invention comprises a component having a functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material, wherein the functional group has one in the molecule.
By using a binder resin bound so as to be 0 ^{-4 to} 5 molar equivalents / kg, the preparation can be further facilitated.

The reinforced inorganic material of the present invention is obtained by applying the above-mentioned inorganic material reinforced paint on the surface thereof, and comprises alkali metal and alkali which are soluble components in the inorganic material which is a substance causing efflorescence. Since the earth metal ion forms a stable complex or chelate compound with the complex forming agent or chelating agent in the inorganic material reinforced paint or a functional group having these functions and conceals it, the influence of the outside air is blocked. In addition, the efflorescence is suppressed, and the inorganic material exhibits sufficient strength by curing, and the deterioration of the inorganic material due to migration of efflorescence and other alkali metal and alkaline earth metal ions is prevented and strengthened.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 5, Comparative Examples 1 to 3) A kneaded product obtained by adding a predetermined amount of water to ordinary Portland cement, fly ash, vinylon fiber and methylcellulose and mixing with a mixer is pressed using a dehydrating press. Molded, 6
An inorganic material was prepared by steam curing at 0 ° C. for 6 hours. The surface temperature of the obtained inorganic material was heated to about 80 ° C., and an epoxy sealer (manufactured by Dainippon Paint Co., Ltd., “V-Selan # 3”) diluted and mixed with a base material: hardener: water = 1: 1: 10 (weight ratio).
50 EP Sealer S ”) with an epoxy impregnated layer of 20 μm
Was applied by airless spray.

After the coating was kept at room temperature for about 60 seconds and the surface temperature of the inorganic material was raised to about 60 ° C., it was applied to a black acrylic emulsion paint (“BR # 10”, manufactured by Dainippon Paint Co., Ltd.).
As a chelating agent, ethylenediaminetetraacetic acid sodium salt (EDTA-4Na) was used.
(The number of moles of the carboxyl group of DTA-4Na) is coated with the inorganic material-enhanced coating material by airless spray so that the film thickness after drying is 60 μm, and baked and hardened in a drying furnace to obtain the strengthened inorganic material. Produced.

[0032]

[Table 1]

With respect to the obtained reinforced inorganic material,
An efflorescence (hereinafter, abbreviated as "Eflo") acceleration test was conducted by the following method. The test results are shown in Table 1.

[Efro-generation rate] One surface of the inorganic material on the day of the material age is coated with the same coating as the above-mentioned reinforced inorganic material, and the uncoated surface is immersed in the water surface and half-submerged.
Let water absorb for 4 hours. The above-mentioned water-absorbed inorganic material is sealed with a film having no moisture permeability, and 50 ° C. × 8 hours → 20 ° C. × 16
A three-hour cooling / heating cycle test was carried out for three hours, opened, and then further sprayed on the painted surface of the inorganic material using a water sprinkler.
Watering was performed for 6 hours at 0 ml / m for ²⁴ minutes and air-dried. After the coated surface was sufficiently dried, the area of the inorganic material generated on the surface of the coated surface was measured to calculate the rate of occurrence of the effluent.

[Coating Adhesion] The obtained reinforced inorganic material is stored for 3 hours in a constant temperature and humidity room at a temperature of 23 ° C. and a humidity of 50% RH, and the adhered dust is wiped off with a clean cotton cloth. Cloth tape (Sekisui Chemical Co., Ltd., adhesive tape "# 60
0 "), and the surface to be adhered is rubbed with a cotton cloth from above to remove air bubbles at the interface. After curing for 6 hours in this state, one end of the cloth tape is pulled with full force and peeled off. Observation of the state of the coating film, ◎: no abnormality was observed at all, も の: substantially no abnormality was observed, Δ: part of the coating was peeled off, ×: most of the coating The film was peeled off and evaluated in four steps.

(Examples 6 to 10 and Comparative Examples 4 to 6) [Preparation of binder resin having EDTA in the side chain] 10 mol of iminodiacetic acid and 16.5 mol of sodium hydroxide were placed in 2 liters of methanol, and The mixture was heated to ° C., and about half of vinylbenzyl chloride (1 mol) was added dropwise over 30 minutes with stirring. Further, 16.5 mol of sodium hydroxide was added, and the remaining half was added dropwise. After the dropwise addition, heating was continued for 30 minutes, and then the mixture was distilled under reduced pressure so that the amount of methanol became 2/3 of the original amount. From the reaction product, vinylbenzyl alcohol and methyl vinyl ether were extracted and removed with ether, and the aqueous solution was adjusted to pH = 2.5 with hydrochloric acid,
A colorless solid precipitated. This was left overnight and filtered to obtain 4050 g of a crude product containing sodium chloride, which was recrystallized from a 10% solution to give 700 g of EDT.
A styrene monomer having A as a side chain was purified.

The obtained styrene monomer having EDTA as a side chain, methyl methacrylate, sodium dodecyl sulfate and 1200 ml of distilled water are stirred at 70 ° C. and about 200 rpm in a vessel equipped with a reflux cooling device. After nitrogen was passed through the vessel, 1 g of ammonium persulfate was dissolved in 20 ml of distilled water, charged into the vessel and reacted for 3 hours to prepare a resin emulsion, and an inorganic material reinforced paint was prepared using the resin emulsion.

Instead of the inorganic material reinforced paint of Example 1,
Except that EDTA was used as a chelating agent and the above-mentioned styrene-methyl methacrylate copolymer resin having a side chain at a ratio shown in Table 2 as a binder resin was used, and a black inorganic material reinforced paint was used in the same manner as in Example 1. , A reinforced inorganic material.

[0039]

[Table 2]

With respect to the obtained reinforced inorganic material,
An Efro acceleration test was performed in the same manner as in Example 1. The test results are shown in Table 2.

[0041]

As described above, the inorganic material reinforced paint of the present invention is constituted as described above. Therefore, when molding the inorganic material, there is no need to use any special equipment such as an autoclave.
In addition, without the need for complicated undercoating, work steps such as topcoating, and furthermore, simply apply to the inorganic material without inhibiting the curing of the inorganic material and affecting the strength development of the cured body. Thus, a reinforced inorganic material capable of reliably and easily suppressing the occurrence of efflorescence can be obtained.

Since the reinforced inorganic material of the present invention is constituted as described above, it exhibits sufficient strength by curing, and at the same time, transfers efflorescence and other alkali metal and alkaline earth metal ions to the inorganic material. Deterioration is prevented and strengthened.

Continued on front page F term (reference) 4G028 CA01 CB01 CD01 4J038 CB001 CD001 CD091 CG001 DB001 DG001 DL031 GA01 GA02 GA03 GA06 GA08 GA09 GA12 GA13 GA14 GA16 JB10 NA02 NA12 PB05 PC04

Claims (4)

[Claims] 1. A complex-forming agent or a chelating agent having a functional group capable of forming a complex or a chelate compound with a cation eluted from an inorganic material, wherein said functional group is 10 ^{-4 to} 5 mol per 1 kg of a binder resin. An inorganic material reinforced paint characterized in that it is contained in an equivalent amount. 2. A component having a functional group capable of forming a complex or a chelate compound with a cation eluted from an inorganic material is bonded to the molecule such that the functional group has a molecular weight of 10 ^{-4 to} 5 mol / kg. An inorganic material reinforced paint characterized by containing a binder resin. 3. A functional group capable of forming a complex or a chelate compound with a cation eluted from the inorganic material is a hydroxyl group, a carbonyl group, a carboxyl group, an ether group, an ester group, a thiol group, a thioether group, a thioaldehyde group, Thioketone group, thiocarbonyl group, thiocarboxyl group, thioamide group, primary amine group, secondary amine group,
Secondary amine group, imine group, amide group, nitro group, nitroso group, N-oxide group, azo group, cyan group, sulfone group,
Phosphone group, phosphine group, primary-, secondary-, tertiary alkyl or allylphosphine group, phenyl group, oxime group, conjugated polyene group, halogen (fluorine, chlorine, bromine,
The inorganic material reinforced paint according to claim 1 or 2, wherein the paint is at least one member selected from an (iodine) group and a Schiff base. 4. A reinforced inorganic material characterized by being coated with the inorganic material reinforced paint according to claim 1, 2 or 3.