JPH03258874A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition useful as heat-resistant coating agent, flame-retardant coating agent, corrosion-resistant coating agent, weather-resistant coating agent, antifouling coating agent, etc., for substrate such as ceramic or concrete, containing a specific peroxy condensed acid, epoxy composition, etc. CONSTITUTION:The objective composition containing (A) a peroxy condensed acid obtained by reacting a transition element (preferably tungsten, molybdenum, vanadium or zirconium) and/or a compound thereof with hydrogen peroxide and (B) an epoxy composition and/or a formalin-based resin composition.

Description

Detailed Description of the Invention [Objective of the Invention] (Scope of Industrial Application) The present invention relates to (A) a peroxide condensed acid obtained from the reaction of a transition element and/or its compound with hydrogen peroxide, and (B) an epoxy The present invention relates to a coating composition containing a composition and/or a formalin-based resin and a substance. More specifically, the peroxide condensed acid obtained from the anti-viscosity of a transition element and hydrogen peroxide acts as a curing agent for a coating composition containing at least an epoxy composition and/or a formalin-based resin composition. This peroxide condensed acid has particularly good compatibility with epoxy compositions and/or formalin-based resin compositions, has a fast curing time, can be applied to water-based and oil-based epoxy compositions and/or formalin-based resin compositions, and is suitable for use in ceramics, concrete, etc. It is extremely useful and can be applied as a heat-resistant coating agent, anti-corrosion coating agent, weather-resistant coating agent, and antifouling coating agent for base materials such as cement, mortar, metal, wood, plastics, fibers, and paper. A coating composition is provided.

(Prior Art) Conventionally, various curing agents for epoxy compositions and/or formalin-based resin compositions have been studied. For example, acidic curing agents such as acid anhydrides, phosphoric acid, p-toluenesulfonic acid, boron trifluoride-acne complex, aromatic diazonium salts, diallyliodonium salts, Lewis acid salts of sodium, tetraethylene pentadanyl, etc. , amines such as triethylene diamine, polyamide resins obtained by condensation of dimer acids and polyamines, various idizoles, alkaline curing agents such as potassium hydroxide and sodium hydroxide, various mercaptans, disindiamide, various hydrazides, etc. It was used. However, most of these curing agents are oil-based, and there are few that can be used as water-based.

In addition, they have various drawbacks, such as a decrease in water resistance due to residual curing agents, poor compatibility with epoxy compositions and/or formalin-based resin compositions, and an inability to maintain a balance between curing time and pot life. Was.

(Solved by the invention! l1a) As a result of intensive studies in view of the above-mentioned drawbacks, it has been found that peroxide condensed acid obtained from the reaction of a transition element and/or its compound with hydrogen peroxide can be used in at least an epoxy composition and/or a formalin-based resin composition. The present invention was discovered to be extremely useful as a curing agent for compositions containing epoxy resins, and the present invention has improved the conventional drawbacks, making it an excellent curing agent for epoxy compositions and/or formalin-based resin compositions, and improving durability. It provides a coating.

Specifically, the peroxide condensed acid obtained from the reaction of transition elements and/or their compounds with hydrogen peroxide can not only be obtained as an aqueous solution, but also dilutable with hydrophilic organic solvents, etc., and is completely soluble in organic solvents. Replacement is also possible. Furthermore, since the peroxide condensed acid has film-forming properties, it has good compatibility with the epoxy composition and/or formalin-based resin M, and a durable film can be obtained. In addition, although the curing is relatively fast, the pot life is relatively long, and water-based,
The present invention provides a coating composition that can be used as a curing agent for oil-based epoxy compositions and/or formalin-based resin compositions, and can be applied to an extremely wide range of uses.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides (A) a peroxide condensed acid obtained from the reaction of a transition element and/or its compound with hydrogen peroxide, and (B) at least an epoxy composition and/or a formalin-based resin composition. The present invention provides a coating composition comprising:

As transition elements, elements with atomic numbers 21 to 29 and 39 to 47 in the periodic table can basically be used.
In particular, tungsten, molybdenum, vanadium, zirconium, etc. are preferred, and compounds thereof can also be used. Specifically, the following can be used, but
It is not necessarily limited to these, but any material that reacts with hydrogen peroxide to give a peroxidized condensed acid may be used.

Tungsten and its compounds include tungsten, tungsten carbide, tungstic acid, tungsten trioxide, tungstic anhydride, tungstic silicoic acid, ammonium metatungstate, ammonium paratungstate, phosphotungstic acid, tungstic silicoic acid, borotungstic acid, and tungstic acid. Lithium, sodium tungstate, potassium tungstate, sodium metatungstate, sodium paratungstate,
Examples include ammonium pentatungstate, ammonium heptatungstate, sodium phosphotungstate, barium borotungstate, and the like.

Molybdenum and its compounds include molybdenum, molybdic acid, molybdic acid dioxide, ammonium phosphomolybdate, ammonium oxychloride molybdate, ammonium metamolybdate, ammonium paramolybdate, phosphomolybdic acid, silicomolybdic acid, boromolybdic acid, and molybdic acid. Lithium, sodium molybdate, potassium molybdate, ammonium heptamolybdate, sodium phosphomolybdate, phosphomolybdic acid, zinc molybdate, calcium molybdate, magnesium molybdate, strontium molybdate,
Examples include barium molybdate.

Examples of vanadium and its compounds include vanadium, vanadium pentoxide, lithium orthovanadate, sodium orthovanadate, lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, and sodium pyrovanadate. It is not limited. For example, it is also possible to use chromium, manganese, iron, cobalt, copper, bismuth, antimony, arsenic, tellurium, etc. instead of phosphorus, silicon, boron, etc. as the different transition element.

Zirconium and its compounds include zirconium nitrate, zirconium sulfate, basic zirconium acetate, zirconium acetylacetonate, ethylenediaminetetraacetate zirconium complex salt, nitrilotriacetate zirconium complex salt, zirconyl chloride, zirconyl nitrate, zirconyl acetate,
Zirconyl salts such as zirconyl sulfate and zirconyl ammonium carbonate can be used, but are not limited to these. Among these, zirconium acid chloride is the most commonly used because it is inexpensive and provides relatively high yield of zirconia.

These transition elements and/or compounds thereof may be used in combination as necessary, under conditions such that a peroxide condensed acid can be obtained by reacting with hydrogen peroxide.

What is important here is that the peroxide condensed acid obtained in the present invention is different from conventional oxyacids or oxyacid salts such as tungstic acid, molybdic acid, sodium tungstate, and sodium molybdate.

That is, many of these oxygen acids do not dissolve in neutral water or hydrophilic organic solvents. Furthermore, although oxyacid salts are not soluble in hydrophilic organic solvents, they are highly soluble in water, so they are mostly used in an aqueous form. on the other hand,
These oxyacids or oxyacid salts do not have film-forming properties. Due to these reasons, the current situation is that there are restrictions depending on the usage.

The peroxide condensed acid obtained by the present invention is considered to be a type of polyacid, but the details are unknown. - Polyacids are generally classified into two types. An acid that is produced by two or more metals is called a heteropolyacid, and is formed by coordinating one metal (or its equivalent) with a central atom and the polyacid group of another metal. It is often done. In contrast to heteropolyacids, acids produced by only one type of metal are called isopolyacids.

Many of the peroxidized condensed acids obtained by the present invention are obtained in the form of amorphous bodies, so their structure is not clear, but peroxo groups (〇-〇) or negative ions such as OH are used directly or in other forms such as water. It is thought that it has a network structure connected through the molecules. Therefore,
The peroxidized condensed acid obtained by this method can be freely mixed with a hydrophilic organic solvent and can even completely replace the organic solvent, and furthermore, this peroxidized condensed acid has film-forming properties. Therefore, it seems to be fundamentally different from conventional oxyacids or oxyacid salts. The peroxide condensed acid in the present invention can be easily synthesized by reacting it with hydrogen peroxide at a temperature ranging from room temperature to 100°C, although it depends on the type of transition element. The hydrogen peroxide used here is a commercially available hydrogen peroxide of about 30 to 60%, which can be used as it is or diluted to an appropriate concentration. The amount of hydrogen peroxide used is approximately 1 gram mole or more per 1 gram atom of the transition metal.

The reaction rate tends to increase as the hydrogen peroxide/transition metal (gram mole/gram atom) ratio increases. It is not very desirable from an economic and safety standpoint to generate a large excess of hydrogen peroxide after the reaction is complete. Therefore, the amount of hydrogen peroxide used is approximately 1 to 5 per gram atom of the transition element.
Preferably, 1.2 to 3 gmol is appropriate. Hydrogen peroxide may be added in its entirety at the start of the reaction, or may be added dropwise little by little while monitoring the progress of the reaction.

The same applies to the method of adding transition metals.

The epoxy composition and/or formalin-based resin composition is not particularly limited, but generally well-known epoxy compositions include bisphenol A-based epoxy resin, novolak-type epoxy resin, bisphenol-F-based epoxy resin, and cycloaliphatic Examples include group epoxy resins, heterocyclic epoxy resins, and the like.

Preferably, a heterocyclic epoxy resin is used. Examples of formalin-based resin compositions include phenol resins and amino resins. Examples of the phenol resin include phenol/formalin resin, cresol/formalin resin, modified phenol resin, phenol/furfural resin, and resorcinol resin. Further, examples of amino resins include urea resins and modified urea resins, melamine resins and modified melamine resins, guanamine resins, aniline resins, and sulfamide resins.

Furthermore, polymers having an N-methylol group or a derivative thereof, an N-alkoxymethyl group, in the polymer molecule can also be used. Moreover, an inorganic compound that reacts with an alkoxy metal such as colloidal silica can also be used in combination, if necessary. Colloidal silica is produced by removing sodium silicate by an ion exchange method, an acid decomposition method, a peptizing method, etc., and is an aqueous dispersion of particles having primary particles of 5 to 1100 nm.

When used, acidic or basic can be selected as appropriate. Examples of acidic products include Snowtex O1 and OL (both trade names, manufactured by Kaguchi Kagaku Kogyo Co., Ltd.); examples of basic products include trace amounts of alkali metal ions, aluminum ions, ammonium ions, or a≧ Colloidal silica stabilized by the addition of
M (all trade names, manufactured by DuPont, USA), Snowtex 20, Snowtex C1 and N (both trade names, manufactured by Yasan Kagaku Kogyo Co., Ltd.), and so on. Preferably, acidic colloidal silica such as Snowtex O or Snowtex OL is desirable. Furthermore, colloidal silica dispersed in a hydrophilic solvent such as alcohol can also be used.

In the present invention, the ratio of the epoxy composition and/or formalin-based resin composition to the peroxide condensed acid is not particularly limited, since the peroxide condensed acid alone has film-forming properties. The amount of the epoxy composition and/or formalin resin composition to be used may be adjusted depending on the intended use.

Furthermore, it is also possible to add various additives depending on the use. Examples include pigments, preservatives, rust preventives, leveling agents, and flame retardants.

The present composition may be applied by conventionally known methods, such as brush coating, spray coating, roll coating, spin coater coating, dip coating, and electrodeposition coating. To cure the composition, approximately 4
It may be dried by heating at a temperature range of 0° C. to 300° C. for about 2 seconds to 30 minutes.

Production examples, examples, and comparative examples are shown below. These examples serve to explain the invention in more detail and are not intended to limit it in any way. Parts and percentages refer to parts and percentages by weight.

Manufacturing example 1 Add 30 parts of a 15% aqueous hydrogen peroxide solution to a beaker.

Thereafter, 8 parts of metallic molybdenum powder were added over 30 minutes. After a vigorous reaction accompanied by foaming, the molybdenum powder was immediately dissolved, and a transparent aqueous solution of acidic, pale yellow peroxidized condensed molybdic acid was obtained. Thereafter, 70 parts of isopropyl alcohol was added and the mixture was left at room temperature for 24 hours.

Production example 2 Put 8 parts of metallic tungsten powder into a beaker, and add 1 part to it.
70 parts of a 5% aqueous hydrogen peroxide solution was added. Through a vigorous reaction accompanied by foaming, the tungsten powder was dissolved in about 30 minutes, and a transparent aqueous solution of acidic, pale yellow peroxidized condensed tungstic acid was obtained. Thereafter, 30 parts of butyl cellosolve was added and the mixture was left at room temperature for 24 hours.

Thereafter, a platinum blackened platinum wire mesh was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 3 Put 6 parts of metal tungsten powder and 2 parts of vanadium pentoxide powder into a beaker, and add 7 parts of 30% hydrogen peroxide aqueous solution to this.
Add 0 parts. The metal powder reacted gradually and dissolved after 30 minutes. A clear aqueous solution of an acidic, pale yellow peroxide condensed acid was obtained. Then, 30 parts of isopropyl alcohol was added.

Production Example 4 10 parts of zirconium acid chloride and 20 parts of ion-exchanged water were put into a flask, the reaction temperature was adjusted to about 50°C, and 15
% hydrogen peroxide was added dropwise over 30 minutes. After 10 minutes of dropping, the mixture was further aged for 1 hour. Thereafter, 100 parts of isopropyl alcohol was added and concentrated using an evaporator. A clear peroxide condensed zirconium alcohol solution of approximately 50% solids was obtained. And 24
It was left at room temperature for an hour.

Production Example 5 Put 8 parts of tungsten carbide powder into a beaker and add 1 part to it.
70 parts of a 5% aqueous hydrogen peroxide solution was added. Through a vigorous reaction accompanied by bubbling, the tungsten carbide powder was dissolved in about 30 minutes, and a transparent aqueous solution of acidic, pale yellow peroxidized condensed tungstic acid was obtained. Thereafter, 30 parts of isopropyl alcohol was added and the mixture was left at room temperature for 24 hours. Thereafter, a platinum blackened platinum wire mesh was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 6 Put 4 parts of ammonium tungstate, 4 parts of metal molybdenum powder, and 20 parts of ion-exchanged water into a beaker, and add 1
Fifty parts of a 5% aqueous hydrogen peroxide solution was added.

Through a vigorous reaction accompanied by bubbling, the metal molybdenum powder was dissolved in about 20 minutes, and a transparent aqueous solution of acidic, pale yellow peroxide condensed acid was obtained. Thereafter, 20 parts of butyl cellosolve was added and the mixture was left at room temperature for 24 hours. Thereafter, a platinum blackened platinum wire mesh was immersed in this to decompose unreacted hydrogen peroxide.

Production Example 7 8 parts of tellurium dioxide powder was taken and suspended in 50 parts of pure water. To this was added 3.9 parts of ammonium paratungstate and melted. This was heated to 90°C, and 30 parts of a 35% aqueous hydrogen peroxide solution was added little by little.

It was completely dissolved after 20 minutes.

Example 1 20 parts of polyvinyl alcohol (trade name GL-05 Nippon Gokai Kagakusei), 90 parts of water, and 10 parts of water-soluble melamine (trade name Sumimaru M-30W manufactured by Sumitomo Chemical Co., Ltd.) were mixed. 5 parts of the solution of Production Example 1 above was added to 50 parts of this solution. Apply this solution to a thickness of about 20μ on a galvanized steel plate and heat it at 150℃ for 2 hours.
When heat treated for 0 minutes, a hard coating film with a pencil hardness of 3H was obtained.

Example 2 Heterocyclic epoxy resin ERL-4221 (manufactured by UCC)
To 50 parts, 30 parts of an isopropyl alcohol solution of colloidal silica having a solid content of 20% was added, and further 10 parts of the solution of Production Example 5 above were added. When this solution was applied to a steel plate to a thickness of about 10 μm and heat treated at 150° C. for 20 minutes, a hard coating film with a pencil hardness of 5H was obtained.

Example 3 10 parts of phenolic resin, 40 parts of liquid epoxy resin, n-
50 parts of butanol were mixed. 5 parts of the solution of Production Example 3 above was added to 50 parts of this solution. Spread this solution on a glass plate for about 20 minutes.
When the coating was applied to a thickness of μ and heat treated at 150° C. for 20 minutes, a hard coating film with a pencil hardness of 3H was obtained.

Example 4 20 parts of 2-hydroxyethyl methacrylate, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2'-azobisisobutyronitrile were prepared with a stirrer, a cooler, and a thermometer. After putting it in a heated flask and purging it with nitrogen, heat it to 80℃±2℃.
Polymerization was carried out at a temperature range of 5 hours to obtain an acrylic resin having a hydroxyl group with a solid content of about 50%. Fifty parts of this solution and 5 parts of butoxymelamine resin were mixed. 5 parts of the solution of Production Example 4 above was added to this solution. Then, this solution was applied to a surface-treated polyester film to a thickness of about 25 μm.
When heat treated at 50° C. for 20 minutes, a transparent coating film was obtained.

Furthermore, with a cloth impregnated with methyl ethyl ketone,
No abnormality was observed even after 0 rubbings.

Example 5 20 parts of N-methoxymethylacrylamide, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2゛azobisisobutyronitrile were placed in a flask equipped with a stirrer, a condenser, and a thermometer. N- with a solid content of approximately 50% was obtained by polymerizing in a temperature range of 80°C ± 2°C for 5 hours after purging with nitrogen.
An acrylic resin having methoxymethyl groups was obtained. To this solution were added 5 parts of the solution of Production Example 6 above. When this solution was applied to a concrete plate with a brush to a thickness of about 25 μm and heat treated at 150° C. for 20 minutes, a hard transparent coating film with a pencil hardness of H was obtained.

Example 6 20 parts of glycidyl methacrylate, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2°-azobisisobutyronitrile were placed in a flask equipped with a stirrer, a condenser, and a thermometer. After replacing the mixture with nitrogen, polymerization was carried out in a temperature range of 80° C.±2° C. for 5 hours to obtain an acrylic resin having an epoxy group with a solid content of about 50%. 5 parts of the solution of Production Example 7 above was added to 50 parts of this solution. When this solution was coated on paper to a thickness of about 15 μm using a bar coater and heat-treated at 150° C. for 20 minutes, a heat-resistant transparent coating film with no blocking was obtained.

Example 7 100 parts of polyvinyl alcohol, 90 parts of water, water soluble 19
1710 parts were mixed. 20 parts of antimony oxide sol solution was mixed with 50 parts of this solution, and 5 parts of the solution of Production Example 1 above was added. After impregnating Kanakin cotton cloth with this solution, it was heat-treated at 150° C. for 20 minutes.

This cotton fabric exhibited very good flame retardancy and good water resistance.

Comparative Example 1 20 parts of polyvinyl alcohol (trade name GL-05 manufactured by Nippon Gokai Kagakusei Co., Ltd.), 90 parts of water, and 10 parts of water-soluble melamine (trade name Sumimaru M-30W manufactured by Sumitomo Chemical Co., Ltd.) were mixed. Apply this solution to a thickness of about 20 μm on a zinc tone plate for 15 minutes.
When heat treated at 0°C for 20 minutes, no hardening occurred.

Comparative Example 2 Heterocyclic epoxy resin ERL-4221 (manufactured by UCC)
30 parts of an isopropyl alcohol solution of colloidal silica having a solid content of 20% was added to 50 parts. Apply approximately 10μ of this solution to the steel plate.
When the coating was applied to a thickness of 100° C. and heat treated at 150° C. for 20 minutes, it did not harden at all.

Comparative Example 3 10 parts of phenol resin, 40 parts of liquid epoxy resin, n-
50 parts of butanol were mixed. When this solution was applied to a glass plate to a thickness of about 20 μm and heat treated at 150° C. for 20 minutes, it did not harden.

Comparative Example 4 20 parts of 2-hydroxyethyl methacrylate, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2°-azobisisobutyronitrile were mixed in a stirrer, a cooler, and a thermometer. After putting it in a flask equipped with
Polymerization was carried out at a temperature range of 5 hours to obtain an acrylic resin having a hydroxyl group with a solid content of about 50%. Fifty parts of this solution and 5 parts of butoxymelamine resin were mixed. Then, this solution was applied to a surface-treated polyester film to a thickness of about 25 μm and heat-treated at 150° C. for 20 minutes to obtain a transparent coating film. Furthermore, when the coated film surface was rubbed with a cloth impregnated with methyl ethyl ketone, the coated film peeled off after just one rub.

Comparative Example 5 20 parts of N-methoxymethylacrylamide, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2゛azobisisobutyronitrile were placed in a flask equipped with a stirrer, a cooler, and a thermometer. N- with a solid content of approximately 50% was obtained by polymerizing in a temperature range of 80°C ± 2°C for 5 hours after purging with nitrogen.
An acrylic resin having methoxymethyl groups was obtained. When this solution was applied to a concrete plate with a brush to a thickness of about 25 μm and heat treated at 150° C. for 20 minutes, a flexible transparent coating film with a pencil hardness of B was obtained.

Comparative Example 6 20 parts of glycidyl methacrylate, 40 parts of butyl methacrylate, 40 parts of methyl methacrylate, 100 parts of isopropyl alcohol, and 1 part of 2.2'-azobisisobutyronitrile were placed in a flask equipped with a stirrer, a condenser, and a thermometer. An acrylic resin having an epoxy group with a solid content of approximately 50% was obtained by polymerizing for 5 hours at a temperature range of 80°C ± 2"C after purging with nitrogen. This solution was coated with a bar coater. When it was coated on paper to a thickness of about 15 microns and heat treated at 150''C for 20 minutes, the coating film was tacky.

Comparative Example 7 20 parts of polyvinyl alcohol (trade name: GL-05 Nippon Hei Kagaku Daiso), 90 parts of water, and 10 parts of water-soluble melamine (trade name: Sumimaru M-30W, manufactured by Sumitomo Chemical Co., Ltd.) were mixed. 20 parts of antimony oxide sol solution was mixed with 50 parts of this solution. After impregnating Kanakin cotton cloth with this solution, it was heated to 150°C.
It was heat-treated for 20 minutes. Although this cotton fabric exhibited very good flame retardancy, its water resistance was significantly poor.

〔Effect of the invention〕

The coating composition obtained in the present invention is Ceramic Tsuku,
Heat-resistant coating agents, flame-retardant coating agents, anti-corrosion coating agents, weather-resistant coating agents, antifouling coating agents for base materials such as concrete, cement, mortar, metal, wood, plastics, fibers, and paper. The present invention provides an industrially extremely useful coating composition that can be applied as a water- and oil-repellent coating agent and a mold release agent.

Claims (1)

[Claims] 1. Contains (A) a peroxide condensed acid obtained from the reaction of a transition element and/or its compound with hydrogen peroxide, and (B) an epoxy composition and/or a formalin-based resin composition. A coating composition characterized by: 2. The coating composition according to claim 1, wherein the transition element is at least one selected from tungsten, molybdenum, vanadium, and zirconium.