JPH0349942B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a long-term rust-preventing coating composition that forms a film with excellent long-term rust prevention properties on steel materials and does not contain volatile components. Conventionally, as a rust-preventive coating composition for steel materials, etc.
Lead-based, chromium-based,
Rust-preventing paints made by mixing anti-rust pigments such as: These paints contain volatile components (solvents)
Since it contains , it poses problems in terms of pollution and health and safety, and it cannot be expected to have very long-term rust prevention properties. In addition, resin linings for the purpose of long-term corrosion and rust prevention of metals are widely used mainly in various pollution prevention devices and chemical equipment, as well as tanks, oil tanks of ships, and ship bottoms. The resin used for these resin linings is unsaturated polyester resin due to its room-temperature curability, on-site workability, and cost.The lining method is FRP lining, that is, organic peroxide is added to the resin in advance before lining construction. It was common practice to mix the materials, apply a sheet-like base material made of glass fiber to the matrix to be lined, impregnate it with the resin using a felt roll or the like, simultaneously defoaming it, and curing it. Recently, in addition to this method, there is a method (flake lining) in which a composition made by blending extremely thin glass flakes with resin instead of glass fiber is applied to the object to be coated with a trowel. It has been put into practical use. For example, such compositions include protective and decorative coating compositions containing fine glass flakes in an organic resin binder vehicle.
51-25368), or a lining material in which glass flakes as a corrosion-resistant material and glass fiber as a reinforcing material are filled in a lining resin (Japanese Patent Application Laid-open No. 52-30855) are known.
In addition, plastics, paints, insulating papers, etc. filled with hydrophobicity and leafing properties are also known by treating the surface of flaky glass with an appropriate substance (Japanese Patent Publication No. 16821/1983). It is being The composition is applied by applying it to the object using a felt roll, trowel, etc., so it is not as easy to apply as ordinary anticorrosion paints, and the construction cost is very high. Currently, it is not widely applied, and as mentioned above, it is used for very limited special purposes. The resin used for these lining materials is generally unsaturated polyester resin, but unsaturated polyester resin uses styrene as a diluent, so it has a strong odor, which poses problems during work, and it is also dangerous. There were problems in that the application was limited due to the short usage time, and in terms of film performance, the alkali resistance was weak. In order to improve the drawbacks of these lining materials that use unsaturated polyester resins as binders, various studies have been conducted on long-term anticorrosion paints that use epoxy resins as binders. Anticorrosive paints that use epoxy resin as a binder are used with the addition of various solvents and reactive diluents in order to achieve a viscosity that allows thick films to be applied. A thick film type anticorrosive paint that is satisfactory in terms of these points has not yet been obtained. The present inventors previously filed an application for a rust preventive composition comprising epoxy resin, glass flakes and/or silica sand, furfuryl alcohol, and a hardening agent, but recently, compositions that can maintain rust preventive properties for a longer period of time have been developed. It has started to be requested. The present invention was made in view of the above-mentioned circumstances, and
In addition to solving the shortcomings of the conventional technology, we aim to provide a long-term rust-preventing coating composition that can form a coating that maintains rust prevention properties for a longer period of time, has good flowability, and does not contain volatile components. It is something to do. That is, the present invention comprises: (A) a main agent formed by adding 50 to 900 parts by weight of a scaly lead alloy pigment and 10 to 50 parts by weight of furfuryl alcohol to 100 parts by weight of an epoxy resin that is liquid at room temperature; B) Concerning long-term anti-corrosion coating compositions comprising hardeners. The epoxy resin used in the present invention has an epoxy equivalent of 150 to 300 and is liquid at room temperature, such as ether type epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, polyphenol type epoxy resins, and aliphatic type epoxy resins. Epoxy resins; ester type epoxy resins such as aromatic type epoxy resins, cycloaliphatic type epoxy resins, and aliphatic type epoxy resins; ether ester type epoxy resins, etc., among which one or more suitable ones can be used. Can be used as a mixture. Among these, bisphenol type epoxy resins and novolak type epoxy resins are preferred. The flaky lead alloy pigment used in the present invention is
Particles made by alloying with Cu, Ni, Sb, etc. are processed together with stearic acid, mineral spirits, etc. into a scale shape using a ball mill, etc., preferably with a particle size of 10 to 100μ and a thickness of 0.5 to 3μ. It is.
Particularly preferred is a scaly lead alloy pigment made of a lead alloy containing 0.05 to 5 weight of one of Cu, Ni, or Sb. The flaky lead alloy pigment used in the present invention can not only impart further rust prevention properties to the coating film by blocking the permeation of corrosive substances, but also impart flexibility to the coating film. Conventionally, compositions using lead in the form of flakes have been known, but by alloying with lead as in the present invention, strength can be imparted to lead particles, and as a result, pigment dispersion in a vehicle during paint production is possible. In the process, deformation, breakage, etc. of the scale-like pigment particles can be prevented. In other words, since the pigment is dispersed in the paint while maintaining an almost perfect scale-like form, the lamination effect in the paint film is further improved, and as a result, the rust prevention properties of the paint film are also improved. From this point of view, the addition ratio of alloying components is
It is preferably 0.05% by weight or more, and preferably about 5% by weight or less in order not to impair the rust prevention properties inherent to lead. In the composition of the present invention, the scaly lead alloy pigment is added to 100 parts by weight of the epoxy resin, which is liquid at room temperature.
It is used in proportions of 50 to 900 parts by weight. In the above range, if the amount of the scaly lead alloy pigment is less than 50 parts by weight, the effect of blocking the permeation of corrosive substances such as moisture will be reduced, and therefore the desired rust prevention property will not be obtained, and on the contrary, the scaly lead alloy pigment will be less than 50 parts by weight. If the lead alloy pigment exceeds 900 parts by weight, the film becomes brittle, which is not preferable. In the composition of the present invention, addition of furfuryl alcohol is essential. This component is used to adjust the viscosity of the composition, but since it has a high boiling point, it has the characteristic that it does not become a volatile component from the film after painting. In other words, furfuryl alcohol has good solubility in the epoxy resin and curing agent, and has the same viscosity-lowering effect as xylene, toluol, methyl isobutyl ketone, butanol, etc., which are generally used as solvents for epoxy resins. Because it has extremely low volatility, there are almost no problems with industrial hygiene or air pollution caused by solvents during painting operations. Further, the furfuryl alcohol remaining in the coating film acts on the plasticizer and has the effect of alleviating the deterioration in physical properties due to curing distortion of thick coating films. By adding this component, one of the characteristics of the composition of the present invention, which is excellent coating workability and contains no volatile components, can be achieved. Furfuryl alcohol is used in an amount of 10 to 50 parts by weight, preferably 15 to 45 parts by weight, based on 100 parts by weight of the epoxy resin which is liquid at room temperature. If the amount of furfuryl alcohol in the above range is less than 10 parts by weight, the viscosity of the composition will be high and the coating workability will be reduced, and if it exceeds 50 parts by weight, the performance such as water resistance of the film will be deteriorated, so both are preferred. do not have. In the rust-preventing coating composition of the present invention, the epoxy resin, which is liquid at room temperature, the scaly lead alloy pigment, and furfuryl alcohol are mixed in a conventional manner to form a main ingredient. If necessary, commonly used coloring pigments, extender pigments, anticorrosion pigments, dispersion aids, suspending agents, diluents, hardening accelerators, etc. may be added to the main ingredient. The long-term rust preventive coating composition of the present invention can be obtained by adding a curing agent to the base agent thus obtained at the time of use. The curing agent for curing the epoxy resin of the present invention may be any curing agent that is generally used as a curing agent for epoxy resins, such as amine adduct resin, polyamide resin, polyamine resin, etc., and may be used alone or as a mixture. These need to have at least two or more nitrogen atoms and an active hydrogen bonded to them in one molecule in order to carry out a cross-linking reaction with the epoxy resin. Particularly preferred curing agents in the present invention include amine adduct resins and polyamide resins made from aromatic amines such as m-phenylenediamine, p,p'-diaminodiphenylmethane, and p,p'-diaminodiphenylsulfone. is preferred. When the amine adduct resin or the like is used as a curing agent, the water resistance of the film can be significantly improved. The curing agent is preferably mixed in an amount of 0.8 to 1.2 active hydrogen equivalents per 1 epoxy equivalent of the epoxy resin. The thus obtained long-term rust-preventing coating composition of the present invention is applied onto steel materials by a conventional method such as brushing, roller, air spraying, etc. to a film thickness of about 0.25 mm to about 6 mm, and then dried at room temperature or by heating. be done. The film obtained after drying has excellent strength and long-term corrosion resistance. Furthermore, when applying the antirust coating composition of the present invention,
It can also be applied on top of an undercoat paint film such as a zinc-rich primer or a wash primer. Furthermore, if necessary, a top coating material such as chlorinated rubber, alkyd resin, epoxy resin, urethane resin, or acrylic resin may be applied onto the coating film obtained from the composition of the present invention. The coating film obtained from the composition of the present invention exhibits excellent adhesion to these top coatings. Thus, according to the antirust coating composition of the present invention,
It is possible to obtain a coating film with excellent long-term rust prevention properties as well as various physical properties. The details of the present invention will be explained below with reference to Examples. "Part" or "%" means "part by weight" or "% by weight"
It is shown with. Example 1 (Main agent) Epoxy resin [Epicote 828: trade name manufactured by Ciel Chemical Co., Ltd.] 60 Titanium oxide pigment 4 Organic bentonite [Bentone #34: trade name manufactured by National Red Co., Ltd.] 2 Furfuryl alcohol 15 Scale-shaped lead alloy pigment A 30 111 (Curing agent) Partially aromatic amine adduct resin [ADEKA HARDENER
EH551: Product name manufactured by Asahi Denka Co., Ltd.] 30 After kneading the main ingredient composition excluding the scaly lead alloy pigment A with a roller, the scaly lead alloy pigment A was added and stirred and mixed with a disper to prepare a main ingredient. A curing agent was stirred and mixed with the base material using a disper to obtain a rust-preventive coating composition of the present invention. After completely removing black scale, rust, and oil from a 150 x 150 x 1.6 mm mild steel plate (JIS-G-3141) by shot blasting, the coating composition was air-sprayed to a dry film thickness of 500μ. Paint as shown, 20℃, 75
It was dried for 7 days at %RH and used for comparative tests. The flaky lead alloy pigment A is made by atomizing a lead alloy containing 0.1% Cu, adding 2% stearic acid and mineral spirits, and
Non-volatile matter processed into scales using a ball mill
88.7% paste with particle size of 10-50μ. Example 2 (Main agent) Part epoxy resin (same as Example 1) 50 Titanium oxide 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 20 Scale-like lead alloy pigment B 30 106 (Curing agent) Part Amine adduct resin (Same as Example 1) 30 A paint was mixed in the same manner as in Example 1, painted and dried in the same manner as in Example 1, and then subjected to a comparative test. The flaky lead alloy pigment B is a paste with a non-volatile content of 90.6% obtained by processing a lead alloy containing 0.1% Ni in the same manner as in Example 1, and has a particle size of 10 to 50μ. Example 3 (Main agent) Part epoxy resin (same as Example 1) 70 Titanium oxide 4 Organic bentonite (Same as Example 1) 2 Furfuryl alcohol 25 Scale-like lead alloy pigment C 35 136 (Curing agent) Part Aromatic amine Adduct resin [Epicure-DX-
103: Trade name manufactured by Ciel Kagaku Co., Ltd.] 30 A paint was mixed in the same manner as in Example 1, applied and dried in the same manner, and then subjected to a comparative test. The flaky lead alloy pigment C is a paste with a non-volatile content of 91.6%, obtained by processing a lead alloy containing 1% Sb in the same manner as in Example 1, and has a particle size of 10 to 50μ. Example 4 (Main ingredient) Epoxy resin (same as Example 1) 70 Titanium oxide 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 25 Scale-like lead alloy pigment A (same as Example 1) 300 401 ( Curing agent) Amine adduct resin (same as Example 1) 35 A coating material was kneaded in the same manner as in Example 1, coated and dried in the same manner, and then subjected to a comparative test. Example 5 (Main ingredient) Epoxy resin (same as Example 1) 70 Titanium oxide 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 30 Scale-like lead alloy pigment B (same as Example 2) 400 506 ( Curing agent) Amine adduct resin (same as Example 1) 35 A coating material was kneaded in the same manner as in Example 1, coated and dried in the same manner, and then subjected to a comparative test. Example 6 (Main ingredient) Epoxy resin (same as Example 1) 60 Titanium oxide 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 20 Scaly lead alloy pigment C (same as Example 3) 350 436 ( Curing agent) Partially aliphatic polyamine (Sanmide T-100: trade name manufactured by Sanwa Kagaku Co., Ltd.) 30 A test piece was prepared in the same manner as in Example 1 and subjected to a comparative test. Comparative Example 1 (Main ingredient) Part epoxy resin (same as Example 1) 70 Titanium oxide 4 Organic bentonite (same as Example 1) 2 Xylol 30 parts Glass flakes [CCF-150: trade name manufactured by Nippon Glass Fiber Co., Ltd.] 25 131 (Curing agent) Part Amine adduct resin (same as Example 1) 35 After kneading the paint in the same manner as in Example 1, it was applied and dried in the same manner and subjected to a comparative test. Comparative Example 2 (Main agent) Epoxy resin (same as Example 1) 60 Titanium oxide 4 Organic bentonite (Same as Example 1) 2 Furfuryl alcohol 25 Talc 50 141 (Curing agent) Amine adduct resin (Same as Example 1) ) 30 parts A paint was prepared in the same manner as in Example 1, applied and dried in the same manner, and subjected to a comparative test. Comparative Example 3 (Main agent) Epoxy resin (same as Example 1) 60 Titanium oxide pigment 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 25 Silane coupling agent [KBM#403: Shin-Etsu Chemical
Co., Ltd. product name] 0.1 Glass flakes [CF-150: Nippon Glass Fiber Co., Ltd. product name] 20 111.1 (Curing agent) Partly aromatic amine adduct resin (same as Example 1) 30 Main agent excluding glass flakes After kneading the blended composition with a roller, glass flakes were added and mixed with stirring using a disper to prepare a base ingredient. A rust-preventive coating composition of Comparative Example 3 was obtained by stirring and mixing the curing agent with the main ingredient using a disper. After completely removing black scale, rust, and oil from a 150 x 150 x 1.6 mm mild steel plate (JIS-G-3141) by shot blasting, the composition was air-sprayed to a dry film thickness of 500μ. 20℃, 75%RH
After drying for 7 days, it was subjected to a comparative test. Comparative Example 4 (Main agent) Epoxy resin (same as Example 1) 60 Titanium oxide pigment 4 Organic bentonite (same as Example 1) 2 Furfuryl alcohol 25 Silane coupling agent (same as Comparative Example 3) 0.1 Granular lead alloy Pigment 20 111.1 (Curing agent) Partially aromatic amine adduct resin (same as Example 1) 30 The granular lead alloy pigment was obtained by atomizing a lead alloy containing 0.1% Cu by an atomization method.
It is a particle of 50μ. This was made into a paint in the same manner as in Comparative Example 3, and a test piece was prepared with a dry film thickness of 500 μm, and was subjected to a comparative test. [Table] [Table] From the above comparative test results table, it is clear that the coating obtained from the coating composition of the present invention exhibits excellent effects in rust prevention, adhesion, impact resistance, etc. On the other hand, the coatings obtained from the comparative compositions containing volatile solvents or from the comparative compositions not containing flaky lead alloy pigments clearly show that they are unsuitable as long-term rust prevention coatings. There is. Furthermore, since the composition of the present invention does not contain any volatile components, it does not pose any health and safety problems during painting operations or problems such as air pollution.

Claims (1)

[Scope of Claims] 1. (A) A base agent made by adding 50 to 900 parts by weight of a scaly lead alloy pigment and 10 to 50 parts by weight of furfuryl alcohol to 100 parts by weight of an epoxy resin that is liquid at room temperature; (B) A long-term anticorrosive coating composition comprising a hardening agent. 2. The long-term rust-preventing coating composition according to claim 1, wherein the scaly lead alloy pigment is made of a lead alloy containing 0.05 to 5% by weight of any of Cu, Ni, or Sb elements. .