JPS6075366A - Rust preventive coating and finishing method - Google Patents

Abstract

PURPOSE:To form a film having excellent rust preventiveness and small electric resistance with high adhesion power on an iron or steel member by coating a zinc rich paint, intermediate paint and cold setting resin compsn. on the surface of said member and drying the same. CONSTITUTION:A film which has excellent rust preventiveness and small electric resistance and does not accumulate the static electricity generated by friction with fluid is formed on an iron or steel part such as a pipe for conveying fluid, etc. A zinc rich paint contg. an epoxy resin, etc as a binder and contg. 80-90% Zn powder in the dry coated film is formed coated dry to 10-70mu thickness and is dried. An intermediate paint consisting of an epoxy resin and a curing agent is then coated thereon and dried. A cold setting resin compsn. consisting of 100pts.wt. a polyester resin, 80-400pts.wt. a pigment consisting of a white pigment and conductive metallic oxide, 0.01-5.0pts.wt. a silane coupling agent and 0.01-10pts.wt. a titanium coupling agent is coated thereon and is dried.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for finishing a rust-preventive coating on a steel structure by forming a strong film with excellent rust-preventive properties and a film exhibiting sufficient electrical resistance to remove static electricity.

Conventionally, various highly corrosion-resistant coating compositions have been applied to steel structures to protect the objects being coated. However, the surface resistance of coating films obtained from commonly used anticorrosion paints showed a high resistance value of 1013 ohms/iq or more, and most of the resistance values were in the range of insulators.

Steel structures coated with such insulators, especially tanks for storing fluids or piping for transporting fluids, are susceptible to friction between the fluid moving inside and the coating light surface. A large amount of static electricity is generated, and the generated static electricity accumulates on the surface of the paint film. As mentioned above, the surface resistance is 10
When exhibiting high insulation properties of ohms/sq or more, the coating film will be charged over a long period of time. Generally, when a good current object comes close to an object charged with static electricity, or due to other accidental causes, the static electricity sparks and is grounded. In particular, flammable combustible substances such as low boiling point and volatile solvents, or crude oil or nuts containing large amounts of these, are particularly useful.
In addition, in tanks that store gasoline, pipes, etc. that transfer gasoline, etc., there is a risk of ignition due to spark discharge, causing an explosion and fire.

Conventionally, in order to remove static electricity, the surface resistance value was set to 1011.
It is known that it is sufficient to set the voltage to about 106 ohms/sq.For this purpose, paints containing conductive metal fine powders such as gold, silver, platinum, copper, and nickel mixed with a color vehicle are used. Paint compositions in which a carbon-based compound having a graphite structure or a non-crystalline carbon exhibiting conductivity is kneaded with a color vehicle are known. However, in the case of the former, there are practical problems because the fine metal powder is very expensive, and it is very difficult to obtain a resistance value (10H to 10' ohm/sq) that is sufficient to remove static electricity. There was a point.

Especially in the case of general-purpose copper and nickel, the potential of the hydrogen electrode is set to O
The voltage of the unipolar potential is Cu/Cu, 0.3
4, Ni/Ni": -0.23, both of which are higher than iron (Fe/Fe++: -0.44). Therefore, when paint containing such substances is applied to the iron surface, the iron There was a major problem in that copper and nickel, which were used as cathodes, corroded more quickly, making them undesirable in terms of corrosion protection.

On the other hand, in the case of a coating composition using a carbon-based conductive substance, the electrical properties are sufficiently satisfied, but as mentioned above, the electrode potential of carbon is higher than that of the material iron, so it may accelerate the corrosion of iron. As a result, there was a problem with corrosion protection.

As mentioned above, in steel structures where static electricity is easily accumulated, there has been a strong desire for coated threads that can prevent fires and explosions caused by static electricity and also have excellent rust prevention properties. At present, a paint system is not available.

In view of the current situation, the present invention aims to eliminate all the drawbacks and problems of the conventional technology, and has excellent rust prevention and static electricity removal properties, as well as ordinary coating film performance such as adhesive strength and durability. The purpose of this invention is to provide a rust-preventing coating finishing method that is as good as or better than other paints.

That is, the present invention provides the following advantages: (1) For iron-copper drawings, the dry coating film has a thickness of io to 70
(11) A step of applying an intermediate coat paint on the zinc rich paint film and drying it, and a step of applying 100% by weight of the resin component on the GiD intermediate coat film. 80 to 400 parts by weight of a conductive white pigment, 0.01 to 5.0 parts by weight of a 7-rank cuffing agent, or 0.01 to 10.0 parts by weight of a titanium cuffing agent. The present invention relates to a rust-preventive coating finishing method comprising the steps of applying a composition and drying it.

The zinc-rich paint used in the present invention is 75 to 95% by weight, preferably 80 to 90% by weight in the dry coating film.
It is an organic or inorganic paint containing zinc powder.

Is it suitable as a vehicle for organic zinc-rich paint? Examples include a combination of xylene resin and polyamide resin, chlorinated rubber, polystyrene resin, silicone resin, etc. Vehicles for inorganic threads such as zinc resin and thibaint include ethyl silicate, sodium silicate, lithium silicate,
Examples include potassium silicate and ammonium silicate.

Particularly preferred vehicles for purposes such as the present invention are epoxy resin-polyamide resin combinations, ethyl silicates, potassium silicates, and tium silicates.

In the finishing method of the present invention, first, the zinc-crystalline paint is applied by spraying, brushing, etc. to the steel surface which has been sufficiently rust-removed by sandblasting or shotblasting.

In the present invention, the thickness of the dry film of the zinc-rich paint is 10 to 70 microns, preferably 15 to 40 microns.
It is micron.

If the film thickness is less than 10 microns, the desired corrosion protection cannot be obtained, and on the other hand, if the film thickness exceeds 70 microns, cohesive failure is likely to occur inside the dry coating layer of the zinc-rich paint. impact, mechanical stress,
A drawback arises in that the film obtained by p1 tends to peel off due to heat shock or the like.

In the finishing method of the present invention, the reason why a zinc-rich paint is particularly used as an undercoat is that the paint dries to the touch very quickly, approximately 5 to 10 minutes, and the surface hardness of the cured film is high. Like undercoats and paint primers used for paints, they dry to the touch for several hours, and their surfaces are sticky and lack hardness, resulting in a high rate of adhesion of dust, sandblasting sand, iron, and iron powder. many,
Moreover, it does not have any disadvantages such as being extremely difficult to clean and removing or causing a lot of damage to the surface of the coating film.

Furthermore, even when exposed outdoors or to rainwater, the cathodic anticorrosion effect of zinc powder allows it to maintain rust prevention for a long period of time.
This allows greater flexibility in the construction process and construction period, and can significantly reduce rusting due to defects in the undercoat and peeling of the topcoat.

In the finishing method of the present invention, after the zinc-rich paint is applied and dried, an intermediate paint is applied. The intermediate paint may be one of the commonly used paints, such as alkyd resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, urethane resin thread paints, and unsaturated polyester paints. Two or more types can be used. Therefore, one of the intermediate coating paints which is particularly preferable for the rust-preventing coating finish of the present invention is an epoxy resin paint consisting of an epoxy resin and a curing agent.

The epoxy resin is a resin having at least two epoxy groups in its molecule, and is preferably obtained by reacting polyhydric alcohol, polyhydric phenol, etc. with excess epichlorohydrin or alkylene oxide. One example is epoxy resin. Examples of polyhydric alcohols are ethylene glycol, propylene glycol, polypropylene glycol, glycerin, neopentyl glycol, butylene glycol, hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol. Polyhydric phenols include 2,2-bis(4-hydroxyphenyl)propane (commonly referred to as nihisphenol), halocunated bisphenol A, 4.4'
-dihydroxyphenylmethane (commonly referred to as bisphenol F), tris(4-hydroxypheny7)
'v) Propane, resorcinol, tetrahydroxyphenylethane, no? These include lac-type polyhydric phenol and cresol-based polyhydric phenol. Examples of epoxy resins other than these that can be used in the present invention include 1,2.3-
) Glycidyl adducts of lis(2,3-epoxyzolopoxy)propane, aniline or aniline conductors (e.g. orntluidine, etc.), phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, etc. glycidyl esters, epoxidized soybean oil, etc. Further, as the curing agent, one or more of amine thread curing agents such as polyamine, polyamide resin, and amine adduct, which are usually used as curing agents for epoxy resins, can be used. Incidentally, when the epoxy resin and curing agent are solid at room temperature, they are used after being dissolved in an organic solvent according to a conventional method.

Another preferable example of the intermediate coating material of the present invention is that 10 to 60 parts of the flat pigment is added to 100 parts by weight of the resin component.
This is a room temperature curable liquid coating composition prepared by adding parts by weight.

The resin component is preferably an unsaturated polyester resin and/or an epoxy resin. The unsaturated polyester resin is preferably a resin that is liquid at room temperature without being diluted with a volatile solvent, and is hardened by a hardening agent or catalyst, and the cured coating film has excellent water resistance and chemical resistance. ing.

Examples of these resins include generally commercially available isophthalic acid-based unsaturated polyester resins, bisphenol-based unsaturated polyester resins, and epoxy acrylate resins.

Examples of the unsaturated polyester resin include Ubica 5523 and 4, manufactured by Nippon U-Pica Co., Ltd., which are generally commercially available as isophthalic acid-based unsaturated polyester resins.
529: Product name Revolac 150 manufactured by Showa Kobunshi Co., Ltd.
HR, etc.: bisphenol-based unsaturated polyester tree f11
Kao Atlas Co., Ltd. mounting product name Atrac 382-05, which is generally commercially available as 1: Showa Kobunshi Co., Ltd. 14
! Product name Rigorac LP-1: Japan Yubika Co., Ltd. Surface product name Yubika 5834, etc.: Kao Aras Co., Ltd. Product name Atra, Ri G-6575: Showa Kobunshi (( 3505: Dow Chemical Co., Ltd. Product name Delakane 5101 411 etc.

These resins usually contain liquid α, β-monoethylenically unsaturated monomers such as styrene and methyl methacrylate in a concentration of 10 to 10%.
It is commercially available containing 50% by weight.

Therefore, in the present invention, the unsaturated polyester resin includes monomers thereof. Further, as the epoxy resin, an appropriate one can be selected from the above-mentioned exemplified epoxy resins, but one that is liquid at room temperature is particularly preferred.

Furthermore, the flat pigment is an extremely thin inorganic flat particle with a thickness of 0.5 to 10 microns and a maximum length of 0.3 to 6 mm, typical examples of which include glass flakes and mica powder. can be mentioned. Particularly preferred are glass flakes. Incidentally, in the case of the above-mentioned unsaturated polyester resin, ketone/perta-oxides such as methyl ethyl ketone peroxide, nohydrocarbon oxides such as cumene hydroperoxide, or peroxy esters such as t-zotylno and monooxyphthalate, etc. In the case of epoxy resin, an amine thread curing agent such as polyamine, amine adduct or polyamide resin is used.Furthermore, particularly preferably, a liquid coating composition curable at room temperature is used as the intermediate coating. As a result, 0.1 to 5.0 parts by weight of a silane coupling agent, which will be described later, can be added and mixed to 100 parts by weight of the resin.

In the finishing method of the present invention, the intermediate coating is applied to a thickness of about 50 to 1000 microns on the zinc-rich paint film, and then dried.

Application methods include conventional methods such as brush, roller, spray, and trowel.

Next, in the present invention, a room temperature curable resin composition composed of a resin, a conductive white pigment, a silane coupling agent, or a titanium coupling agent is applied. The resin component in the room-temperature curable resin composition is the above-mentioned epoxy resin, unsaturated polyester resin, etc., which is a resin used for ordinary paints that is cured by a curing agent or catalyst, and the cured coating film is water resistant. Suitable materials include those with excellent chemical resistance and chemical resistance. Preferred examples include bisphenol-type epoxy resins,
These are unsaturated polyester resins (containing unsaturated monomers) such as isophthalic acid-based unsaturated polyesters, bisphenol-based unsaturated polyesters, and epoxy acrylates. These are cured using a curing agent as described above.

The conductive pigment used in the room-temperature curable resin composition of the present invention is white and has an average particle size of 5 microns or less.

The pigment includes In on the surface of the white pigment of titanium oxide cape.
Examples include those in which a film of conductive metal oxide such as 2O, SnO2, 5b205 is formed, or a mixture of both (containing 20 to 90% by weight of conductive metal oxide). Particularly in the present invention, the former pigment is preferred. Suitable pigments include conductive white powders W-1 and W-2 manufactured by Mitsubishi Metals Co., Ltd. The mixing ratio of the resin component and the conductive white pigment in the present invention is 80 to 400 parts by weight, preferably 10 to 100 parts by weight of the former.
It is 0 to 350 parts by weight. If the amount of the conductive white pigment is less than 80 parts by weight in the above mixing ratio, the surface resistance of the formed coating film will be 10 ohm/sq or more, and it will not be possible to obtain a resistance value sufficient for removing static electricity. If the amount exceeds 400 parts by weight, the coating film becomes brittle and the rust prevention properties decrease, both of which are undesirable.

Further, as the silane cassilling agent used in the room temperature curable resin composition of the present invention, for example, the general formula (where R1 is a divalent hydrocarbon group having 1 to 4 carbon atoms, R2
and R3 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, 2 is a hydrogen atom or an aminoalkyl group, m is 1 or O)
or an aminoalkoxysilane compound represented by the general formula (where R4 is a divalent hydrocarbon group having 1 to 4 carbon atoms, R5
and R6 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, Q is a methacryloxy group, acryloxy group, glycidoxy group, or epoxycyclohexyl group, and n is an alkyl alkoxysilane compound represented by 1 or O. be.

Specific examples of the former compound include aminemethyltriethoxysilane, N-(β-aminoethyl)aminemethyltrimethoxysilane, aminemethyljethoxysilane, and N-(β-aminoethyl)aminemethyltrimethoxysilane.
-(aminoethyl)aminemethyltriptoxysilane,
γ-aminozolopyltriethoxysilane, γ-aminozolobylmethyljethoxysilane, γ-aminoisobutyltrimethoxysilane, N-(β-aminoethyl)-γ-
Examples include aminoglobil trimethoxysilane and N-(β-aminoethyl)-γ-aminozorobylmethyldimethoxysilane.

Specific examples of the latter compounds include γ-glycidoxyglobyltrimethoxysilane, r-glycidoxynorobylmethyldimethoxysilane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4epoxycyclohexyl)ethyltrimethoxysilane,
Examples include 4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4epoxycyclohexyl)ethylmethyldimethoxysilane, and γ-methacryloxyglobyltrimethoxysilane. Furthermore, other silane cutting agents containing a vinyl group such as vinyltriethoxysilane and vinyltris-β-methoxyethoxysilane are also included in the present invention. The above-mentioned silane coupling agents can be used alone or as a mixture of two or more. In the present invention, among the silane coupling agents, it is particularly preferable to use an alkoxysilane compound represented by the formula (2), and more preferably β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- The use of glycidoxyprobyltrimethoxysilane and gamma-methacryloxyglobyltrimethoxysilane is preferred.

In addition, organometallic compounds such as dibutyltin dilaure-1 and diptyltin di(
2-ethylhexoate), stannous oleate, tin naphthenate, stannous chloride, tin chloride, etc. can be added in an amount of 1% by weight or less.

The silane cassilling agent is used in an amount of 0.01 to 5.0 parts by weight, preferably 0.1 to 0.0 parts by weight, per 100 parts by weight of the resin component.
It is added in a proportion of 2 parts by weight.

These silane cassilling agents further improve the adhesion of the room-temperature curable resin composition to the zinc-rich paint, contributing to improved anticorrosion performance, and also combine with the conductive white pigment, which is an inorganic material, in the resin composition. This helps to improve the compatibility with the resin component, which is an organic material, and therefore it is possible to improve the physical and chemical properties of the resulting film.

Furthermore, examples of the titanium coupling agent used in the room temperature curable resin composition of the present invention include inglobil triinstearoyl titanate, inglobil triinteroctanoyl titanate, inpropyl diinstearoyl cumylphenyl titanate, and inglobil distearoyl methacrylate. Titanate, inglovir dimethacrylylisostearoyl titanate, inglovir tridodecylbenzenesulfonyl titanate, isopropyl diisostearoyl acrylic titanate, inpropyl isostearoyl diacryl titanate, inpropyl tris(dioctyl phosphate) titanate, inzolopyl tris(n)
-stearoyl titanate, Improvil 4-aminebenzenesulfonylbis(dodecylbenzenesulfonyl)
titanate, inglobil tricumylphenyl titanate, inpropyl tri(4-aminobenzoyl) instearoyl titanate, inpropyl tris (dioctyl pyrophosphate) titanate, inpropyl tris (octyl butyl pyrophosphate) titanate,
Tetrainpropyl bis(dilauryl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate), tetraisopropyl bis(ditridecyl phosphite) titanate, tetra(2,2 diallyloxymethyl-1-butoxy) bis( ditridecyl) phosphite titanate, diisostearoyloxyacetate titanate, instearoyl methacryloxyacetate titanate, instearoyl acryloxyacetate titanate, bis(dioctyl phosphate) oxyacetate titanate, 4-aminopenzoyl isostearoyloxyacetate titanate, bis(dioctyl pyro phosphate) oxyacetate titanate, bis(octylbutyl/(ylophosphate)oxyacetate titanate, diisostearoyl ethylene titanate, instearoyl methacryl ethylene natanate, bis(dioctyl phosphate) ethylene titanate, 4-aminobenzoyl instearoyl ethylene titanate, bis (dioctyl pyrophosphate) ethylene titanate, inpropyl tri(N-aminoethyl aminoethyl (titanate), dicumylphenyloxyacetate titanate, etc.) These titanium coupling agents may be used alone or as a mixture of two or more. In the present invention, among the titanium coupling agents, inglobil triisostearoyl titanate, inglobil tridodecyl benzenesulfonyl titanate, isopropyl tris(dioctyl phosphatate) titanate, bis(cyoctyl or irophosphene) are used. ) oxyacetate titanate,
Bis(dioctyl pyrophosphate) ethylene titanate, inglobiltrioctanoyl titanate, isopropyl dimethacrylylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N- aminoethyl (aminoethyl) titanate, dicumylphenyloxyacetate titanate,
The use of one or a mixture of two or more diinstearoyl ethylene titanates is preferred. The titanium coupling agent may be used in an amount of 0.01 to 100 parts by weight of the resin component.
It is used in a proportion of 10.0 parts by weight, preferably 0.1 to 8.0 parts by weight. The titanium coupling agent also has the same effect as the silane coupling agent, and can improve the physical properties of the coating layer.
Chemical properties can be improved. If the amount of the silane coupling agent and titanium coupling agent added is less than 0.01 parts by weight, the effects of the present invention cannot be achieved, and if the amount of the silane coupling agent and titanium coupling agent is less than 0.01 parts by weight, the effects of the present invention cannot be achieved. , the titanium coupling agent is 10.
If more than 0 parts by weight is used, the rust prevention properties of the resulting film will deteriorate, so it is preferable.

The room-temperature curable resin composition of the present invention may be mixed with an organic solvent, a reactive diluent, etc. for dispersion of pigments or as necessary for coating workability.

In addition to the above-mentioned additives, general coloring pigments, extender pigments, dispersion aids, suspending agents, dryers, curing accelerators, etc. are added to the room temperature curable resin composition used in the present invention by a conventional method. I can do it.

The thus obtained room temperature curable resin composition is coated with a curing agent such as an inorganic peroxide to form a film thickness of 5 ml on the intermediate coating film.
It is applied to a thickness of 0 microns or more. Application methods include conventional methods such as brush, roller, spray, and trowel.

If the film thickness of the resin composition is substantially 50 microns or more, it is not very effective as a rust-preventing coating, which is the object of the present invention.

The film obtained by the method of the present invention as described above not only has excellent static electricity removal properties and anti-corrosion properties, but also has improved interlayer adhesion, so that the physical properties of the film as a whole are improved.
Because of its improved chemical performance, it is extremely useful as a rust-preventive coating for steel structures.

The details of the present invention will be explained below using examples.

"Part" or "ch" indicates "1 part by weight" or "wt%".

Prior to the Examples, a siding rich paint, an intermediate coating, and a room temperature curable resin composition were prepared using the following formulations.

[Formulation l]

Sodium silicate aqueous solution (solid content 40%) 30 parts zinc powder
70 [Formulation 2] Ethyl silicate solution 25 parts zinc powder 75 Ethyl silicate solution is manufactured by Nippon Colcoat Co., Ltd. under the trade name Colcoat 40 [solid content 40% alcohol solution; linear and branched tetraethyl orthosilicate with an average degree of condensation of about 4 to 5. A condensation polymer] was used.

[Formulation 3] (Main ingredient) Epoxy resin 6 parts Kijiroru 1O Methyl innotyl ketone 9 Zinc dust 65 (Curing agent) Polyamide resin 4 Kijirole 4 Inbutanol 2 The above epoxy resin is manufactured by Shell Chemical Co., Ltd.! 7! Product name: Ebi Cortona 1ooi (epoxy equivalent: 450-520),
The polyamide resin is manufactured by Fuji Kasei ■ Part name: Tomide Donna 21
0 [amine value 95±5] was used.

The above formulations 1 to 3 are formulations of sink-rich paint, and each is mixed with zinc dust or zinc dust and a curing agent at the time of use.

[Formulation 4] (Main ingredient) Isophthalic acid-based unsaturated polyester resin 50 parts Organic bentonite (anti-settling agent) 35 7 Gin coupling agent 0.1 Styrene 25.7 Copal nanthenate) (6!J containing metal cobalt') 0
．． 7 Glass flakes 20 (Curing agent) Methyl ethyl ketone/4'-oxide 0.7 The unsaturated polyester resin is Showa Kobunshi ■ Surface product name Sugora,
150HR, organic pentonite (product name: Pentonna 34 manufactured by National Red Co., Ltd.), silane coupling agent (product name: KBM5O3 [γ-methacryloxyglobyltrimethoxysilane] manufactured by Shin-Etsu Chemical Co., Ltd.), and glass flakes. Product name: CF-150 manufactured by Nippon Glass Fiber Co., Ltd.
were used respectively.

[Formulation 5] (Main ingredient) Epoxy acrylate resin 60 parts Umeki bentonite (same as formulation 4) 3.5 Silane coupling agent 0.2 Styrene 2o, 5 Cobalt naphthenate (same as formulation 4) 0.8 Glass flakes ( Same as formulation 4) 15 (Curing agent) Methyl ethyl ketone peroxide 1.2 The epoxy acrylate resin is manufactured by Showa Kobunshi Co., Ltd., part name: Lipoxy R-806, and the silane coupling agent is manufactured by Shin-Etsu Chemical Co., Ltd., part name: KBM+303. (β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane) [Formulation 6] (Main ingredient) Epoxy resin (same as formulation 3) 30 parts Organic bentonite (same as formulation 4) 2 xylene 16 Methyl ingutyl ketone 6 Glass flakes (same as formulation 3) 14 (curing agent) yI?Liamide resin (same as formulation 3) 20 xylene 6 Isobutanol 6 [Formulation 7] (Main ingredient) Epoxy resin (same as formulation 3) 24 Titanium oxide 24 Methyl ethyl ketone 8 Cyclohexane 8 Xylene 16 (Curing agent) Polyamide resin 12 Methyl ethyl ketone 2 Cyclohexane 2 Xylene 4 The polyamide resin used was Daiichi Kogyo Seiyaku Kogyo Co., Ltd. (trade name: Persamide 115).

The formulations 4 to 7 are intermediate coating formulations, in which the main ingredient and curing agent are mixed together before use.

[Formulation 8] (Main ingredient) Organic bentonite (same as formulation 4) 2.7 Silane cutting agent (same as formulation 4) 0.1 Styrene 16 Cobalt heptanoate (same as formulation 4) 0.7 Conductive white Pigment 5゜ (hardening agent) Methyl ethyl ketone peroxide 0.7 The conductive white pigment used is Mitsubishi Metals' product name W-1 [a conductive film of tin oxide and antimony oxide is formed on the surface of fine titanium oxide powder]. did.

[Formulation 9] (Main ingredient) Epoxy acrylate resin (same as formulation 5) 30 Dilute organic bentonite (same as formulation 4) 2.7 Silane coupling agent (same as formulation 5) 0.2 Styrene 11.2 Cobalt naphthenate ( Same as formulation 4) 0.7 Conductive white pigment (same as formulation 8) 54 (Curing agent) Methyl ethyl ketone peroxide 1.2 [Formulation 1o
) (Main ingredient) Epoxy resin (same as formulation 3) 15 Organic Pe/tonite (same as formulation 4) 1 Kijirol 1
8 Methyl isobutyl ketone 5 Titanium coupling agent 1 Conductive white pigment 60 (Curing agent) Polyamide resin (same as formulation 3) 10 Kijirol 2
Fisoptanol 13 The titanium coupling agent is Pre/Act KR-28 [isopropyl octanoyl titanate] manufactured by Ajinomoto Co., Inc., and the conductive white pigment is titanium oxide [Titan Kogyo Co., Ltd.].
Co., Ltd.'s product name n-30] and a transparent conductive metal oxide [Mitsubishi Metals Co., Ltd. product name T-1 = mixture of tin oxide and antimony oxide] in a ratio of 3 = 1 (weight ratio). ◎ [Formulation 11. ) (Main ingredient) Organic bentonite (same as formulation 4) 2.7 Silane coupling agent (same as formulation 4) l Styrene 11 Cobalt naphthenate (same as formulation 4) 0.7 Conductive white pigment (same as formulation 8) 60 (Curing agent) Methyl ethyl ketone peroxide 0.6 [Formulation 12
] (Main ingredient) Organic pentonylate (same as formulation 4) 2.7 Titanium coupling agent 2 Styrene 13 Cobalt nanthenate (same as formulation 4) 0.7 Conductive white pigment (same as formulation 8) 55 (Curing agent ) Methyl ethyl ketone peroxide 0.6 The titanium coupling agent used was Zolenact KR-38S (Inzolobiltris (dioctyl pyrophosphate) titanate) manufactured by Ajinomoto Co., Inc.

[Formulation 13] (Main ingredient) Epoxy resin (same as formulation 3) 30 Decomposer bentonite (same as formulation 4) 1 Kizilol 19 Methyl isobutyl ketone 5 Carbon black 5 Talc 40 (Curing agent) Polyamide resin (same as formulation 3) 20 Kijiroru 20 Isobutanol 10 The above formulations 8 to 13 are room temperature curable wood 11f compositions, and each component of the ojiju agent was kneaded in a Nigu, and then mixed with a curing agent at the time of use.

Example 1 150X150XO, Muyo mild steel plate (JIS-G-31
41) was shot blasted to completely remove black skin, rust, and the like, and then painted with the above formulation 1 using air spray to a dry film thickness of 40±5 microns, and heated at 20°C.
A zinc-rich paint film was obtained by drying at 75% RH for 7 days. Then, apply formulation 4 on top of it to a dry film thickness of 500±
After coating to a thickness of 50 microns and drying at room temperature for 7 days, Formulation 8 was coated to a dry film thickness of 50±5 microns and finished by drying at room temperature for 7 days.

Example 2 Formulation 2 was applied onto the same substrate as in Example 1 to a dry film thickness of 40
After coating to a thickness of ±5 microns and drying, the above formulation 5 was applied in the same manner and allowed to dry. Next, Formulation 9 was applied so that the dry film thickness was 100 ± lO microns, and after drying, it was subjected to a comparative test. Example 3 Formulation 3 was applied on the same substrate as in Example 1, After drying, Formulation 6 was applied in the same manner. Next, the blended IO was applied to give a dry film thickness of 50±5 microns, and after drying, a comparative test was conducted in the same manner.

Example 4 Formulation 1 was applied onto the same object as in Example 1 and after drying, the dry film thickness of Formulation 7 in one application was 150±20
It was applied twice to a micron thickness and similarly dried for 7 days. However, the second coat was applied 24 hours after the first coat. Formulation 11 was then applied and dried in the same manner as described above, and then subjected to a comparative test.

Example 5 Formulation 2 was applied onto the same substrate as in Example 1 and dried, and then Formulation 7 was applied and dried in the same manner as in Example 4. Formulation 12 was then applied and dried in the same manner as described above, and then subjected to a comparative test.

Comparative Example 1 Formulation 1 was applied in the same manner as in Example 1 on the same substrate as in Example 1, and after drying, Formulation 4 was applied to a dry film thickness of 550±50 microns and dried in the same manner. , and then subjected to a comparative test.

Comparative Example 2 Formulation 2 was applied on the same substrate as in Example 1 and dried in the same manner as in Example 2, and then Formulation 5 was applied in the same manner as in Comparative Example 1, and after drying, a comparative test was conducted.

Comparative Example 3 On the same substrate as in Example 1, Formulation 3 was applied and dried in the same manner as in Example 3, and then Formulation 6 was applied in the same manner as in Comparative Example 1, and after drying, it was subjected to a comparative test. .

Comparative Example 4 Formulation 1 was applied and dried on the same substrate as in Example 1, and then Formulation 7 was applied so that the dry film thickness in one application was 1.
Example 4
It was applied in the same manner as above, and after drying, it was subjected to a comparative test.

Comparative Example 5 On the same substrate as in Example 1, Formulation 1 was applied and dried, and Formulation 4 was similarly applied and dried.

Formulation 13 was then applied in the same manner and after drying was subjected to a comparative test.0 Comparative test results 2000 hours @ fog.

Note 2) After the salt spray test, the trial piece was painted)
The paint film was peeled off and the progress of rust in the scratched area was measured, and the average value was calculated.

Note 3) The surface resistance value of the coating film was measured.

The comparative test results clearly show that the coating obtained by the finishing method of the present invention had both rust prevention properties and a resistance value sufficient to eliminate static electricity. On the other hand, the films obtained in Comparative Examples 1 to 4 had high resistance values and were insufficient for removing static electricity, and the films obtained in Comparative Example 5 had significantly poor rust prevention properties. However, a product with both properties could not be obtained.

Written Amendment of Procedural Amendment 59 March 9th Director of the Japan Patent Office Kazuo Wakasugi 1 Indication of Case 41 Title 180824/1982 26 Name of Invention Rust-preventive Coating Finishing Method 3 Person Making Amendment Relationship with Case Patent Appearance Person name (332) Dainippon Toyo Co., Ltd. 4 Agent address 5-13 Toranomon, Minato-ku, Tokyo 110 Toranomon
Scope of Claims and Detailed Description of the Invention in Mori Building Specifications Column 1, Scope of Claims? Please make corrections as shown in the attached sheet.

2. Akira <(Item F in the book? Correct as follows.

il+ The [ in line 400 and 20 was almost there. J? ``It was very difficult,'' he said.

(2) In the 5th stroke, line 9, select one good-observation body "good-conducting ε-body".

(3) r Cu/Cu++ on page 6, line 11: 0.34
, Ni/Ni++ knee 0.23 J 'l r C
u/Cul+: +0.34mV, Ni/Ni←knee 0
．． 23mV J and 6° (4) Page 6, line 11 r (F e/F e→knee 0.4
4) l4r(Fe/Fe4+: -0,44mV
) I and 6° (5) “Steel structure” on page 7, line 2? "
"Steel structure".

(0) In lines 12 and 13 of the 10th line, ", apply cloth." is changed to 1. (7) In the 11th ffllO line, 1 glycerin is deleted.

18) Page 16, line 14, "A5 or both?" Ge [or white pigment and conductive gold tetraoxide 71ξ].

19) Page 19, line 3 r(3,4 epo 1 kerr(3,4-
Epo and f stone.

(1■ Page 19, line 4 r(3,4EvoJ=27(3,
4-Evo”.

Ut+ page 19, line 5 r(3,4 epo IYr(3,
4-Evo”.

+I2) “0.2 part by weight” on page 20, line 8? [2,0
Let the weight be part J.

113) Page 20, line 14, “Compatibility” game “Affinity 1 and 'fro.

U 滲 Page 22, line 1 r (2, 27 ant 47r (2,
2-Noari” and 5°+1!19 “-1 Gutoxy” on page 22, line 2) 1 [
-1-butoxy) 1 and f.

+16) m22g19 line [aminoethyl (titanate, "? [aminoethyl)titanate, 1 and teru.

(in Page 24, line 14, [Coating workability 1] "Painting workability is 1.

+teJ, page 26, line 15, ``71 methyl isozotyl ketones [1 methyl isobutyl ketone].

tll 28th nail, row 20 r (3,4 eba? Gizo-1?
r(3,4-epoxy 7,1 and fro.

(For 11-A steel structures, the thickness of the dry coating is 10 to 7
Apply non-flitch paint χ so that it is 0 microns,
Drying step, + ii) Applying an intermediate coat on the non-flitch paint film and drying, and (iii) Adding 80 to 80 to 100 parts by weight of a conductive white pigment per 100 parts by weight of the resin component on the intermediate coat film. 4.00 parts by weight, 0.01 to 5.0 parts by weight of a silane coupling agent, or 0.01 to 10.0 parts by weight of a titanium coupling agent, and applying a room temperature curing resin composition and drying. , Rust-proof coating finishing method.

(2) Is non-clinch paint work? The antirust coating finish according to claim 1 (()), which uses ethyl silicate, potassium silicate, or IJ aluminum silicate as a binder, and contains 80 to 90% by weight of zinc powder in the dry coating film. Method.

13+ The rust-preventive coating method according to claim (1), wherein the intermediate coating is an epoxy resin coating comprising an epoxy resin and a curing agent.

(111 Intermediate paint is a room-temperature curable liquid paint composition comprising 10 to 60 parts by weight of a flat pigment based on 100 parts by weight of a resin component. Coating finishing method.

(5) The rust-preventing coating finishing method according to claim (4), wherein the resin component of the intermediate coating is one or a mixture of two or more of liquid unsaturated hysteryl ester resins or epoxy resins.

(6) The anticorrosive coating finishing method according to claim (4), wherein the flat pigment is a glass flake having a thickness of 0.5 to 10 microns and a thickness of 0.3 to 6 microns.

(Sword Room Temperature Curing 411) is a method for finishing a rust preventive coating according to claim 11.1, wherein the resin component in the composition is an unsaturated yj?+7 esthetic/I/ resin and/or an epoxy resin.

(8) Is the conductive white pigment a film of conductive metal oxide on the surface of the white pigment? Claim No. 11 which is a pigment formed or a mixed pigment of a white pigment and a conductive metal oxide
Rust-preventive coating finishing method described in section.

(9) The silane coupling agents are β-(3,4-epoxycyclohexyl)ethyltrimethoxy7silane and γ-glycidoxyzorobyltrimethoxy7silane.

or 1 fJti of r-methacryloki71ropitrimethoxysilane, or a mixture of two or more thereof.

0α Titanium cassilling agents are isopropyltriinoste rI:1 titanate, isopropyl tridodecyl lebenzenesulfonyl titanate, and Ia f.

Bitris(nooctylpyrophosphate) titanate, bis(nooctylnoylophosphate) A-quinol acetate titanate, bis(nooctylnoylophosphate) ethylene natanate, isopropyltrioctanoyl titanate, isozoro and M nomethacrylic isostearoyl titanate.

Inglobil inostearoylnoacrylate A/titanate, isozolopyrtri(nooctylbosphate) titanate, isoprobil tricumylpheni titanate, isozolopyrtri(N-a is noethyl-ami/ethyl) titanate, tsucumylphenyloxyacetate titanate, noiso 112. The rust-preventive coating finishing method according to claim 111, which is a mixture of one or more types of stearoyl ethylene timenate.

0υ Dedicated white pigment is a white pigment with a film of In2O3゜SnO or 5b203 formed on the surface.
A rust-proof coating finishing method according to claim 111.

Claims (1)

[Claims] (1) For medium steel structures, the dry coating film has a thickness of 10 to 7
Apply zinc rich wave in) so that it is 0 microns,
(11) A step of applying an intermediate coating paint on the zinc-acrylate paint film and drying it; 400 parts by weight, 0.01 to 5.0 parts by weight of a silane coupling agent or 0.01 to 10.0 parts by weight of a titanium cassyl cylinder agent is applied, and drying. (2) The zinc-rich paint uses epoxy resin, ethyl silicate, potassium silicate, or lithium silicate as a binder, and contains 80 to 90% by weight of zinc dust in the dry coating film. The rust-preventive coating finishing method according to claim (1). (3) The rust-preventive coating method according to claim (1), wherein the intermediate coating is an epoxy resin paint consisting of an epoxy resin and a hardening agent. 4) The rust-preventing coating finish according to claim (1), wherein the intermediate coating is a liquid coating composition curable at room temperature, in which 10 to 60 parts by weight of a flat pigment is added to 100 parts by weight of a resin component. Method. (5) The rust-preventive coating finishing method according to claim (4), wherein the resin component of the intermediate coating is one or a mixture of two or more of liquid unsaturated polyester resins or polyester resins. (6) The rust-preventive coating finishing method according to claim (4), wherein the flat pigment is glass flakes having a thickness of 0.5 to 10 microns and a size of 0.3 to 6 In. The rust-preventive coating finishing method according to claim (1), wherein the resin component in the curable resin composition is an unsaturated polyester resin and/or an epoxy resin. (8) The conductive white pigment coats the surface of the white pigment. Claim No. (1) which is a pigment in which a film of a conductive metal oxide is formed on a pigment, or a mixed pigment of a white pigment and a conductive metal oxide.
Rust-preventive coating finishing method described in section. (9) The silane coupling agent is one or more of β-(3,4 epoxycyclohexyl) ethyltritoxysilane, γ-glycidoxyprobyltrimethoxysilane, or r-methacryloxyglobyltrimethoxysilane, or 2wi or more. The rust-preventive coating finishing method according to claim (1), which is a mixture. OQ titanium coupling agent is isoglobil triine stearoyl titanate, isozolobil tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate , isopropyl trioctamale titanate, isoglobil dimethacrylic instearoyl titanate,
isopropyl isostearoyl diacrylic titanate,
Patent for one or a mixture of two or more of isopropyl tri(dioctyl phosphate) titanate, inglobil tricumylphenyl titanate, isopropyl tri(N-aminoether aminoethyl) titanate, dicumylphenyloxyacetate titanate, diinstearoyl ethylene titanate A rust-preventive coating finishing method according to claim (1). ell) A conductive white pigment is placed on the surface of the white pigment.
205 #S n O2 or 5b2o.