JPS61107981A - Method for forming corrosion-proof film - Google Patents

Abstract

PURPOSE:To prevent the lifting of a film, by coating a base material with epoxy resin under coat containing an amine curing agent to form a coating layer and subsequently applying a room temp. curable solventless oil modified alkyd resin paint containing a metal desiccant mixture. CONSTITUTION:Epoxy resin under coat containing an amine curing agent is applied to the metal base material of a plant or ship and dried to form an under coat layer. Subsequently, top coat, which is prepared by compounding 0.3-3pts.wt. of a metal desiccant mixture (consisting of 0.01-1pts.wt. of organocobalt carboxylate, 0.01-1pts.wt. of organolead carboxylate and 0.0001-1 pts.wt. of organometal carboxylate containing a metal selected from Mn, Ca, Zr and Fe) with 100pts.wt. of a radical polymerizable or oxidation polymerizable solventless oil modified alkyl resin paint composition, is applied and subsequently dried to form a cured film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coating method for forming an anticorrosive coating on plants, ships, etc.

[Prior art]

An epoxy resin undercoat film is formed on a base material such as metal, and then a solvent-based oil-modified alkyd resin paint or an air-drying solvent-free oil-modified alkyd resin paint that is capable of radical polymerization and oxidation is applied, and then air-dried. It is known that a heavy anticorrosive coating film can be formed by applying this method (see JP-A-59-123572, JP-A-59-123573, and JP-A-59-13270).

The latter solvent-free oil-modified alkyd resin paint has the advantage of providing a thick film with excellent bending resistance and corrosion resistance compared to solvent-based paints.

[Problems with conventional technology]

The painting method using this epoxy resin undercoat paint starts from spring.
The problem does not occur until autumn, but when painting is carried out during the severe cold period of winter ('rm degree is 5 degrees Celsius or less), peeling occurs between the epoxy resin base coat film and the oil-modified alkyd resin film, causing floating. It was observed that an upward shift (so-called lifting) phenomenon occurred.

The cause of such lifting is that when an oil-modified alkyd resin paint that hardens at room temperature through radical polymerization is applied directly onto an epoxy resin undercoat film containing an amine-based hardener, unreacted amines, which are the epoxy resin hardener in the undercoat paint, are applied. This is presumed to be due to the sudden decomposition of peroxide, which is a radical polymerization initiator in oil-modified alkyd resin paints, resulting in poor curing of oil-modified alkyd paints (
There are 11 theories claiming that

According to our tests, even if the undercoat epoxy resin film was not sufficiently cured, no lifting was observed in the topcoat when an oil-modified alkyd resin topcoat was applied on top of the undercoat epoxy resin film. However, when applying Doryu paint many times to obtain a thick coating film, if the top coat applied the first time was not sufficiently cured (it was dry to the touch), the second coat was applied.
It was found that lifting occurred when the second top coat was applied. To prevent this, increasing the amount of cobalt naphthenate, which is a drying agent, will improve the drying properties of the surface coating, but if the second top coat is applied while the inside of the coating is still uncured. It has been found that lifting cannot be prevented.

[Specific measures to solve the problem]

The above-mentioned problem of lifting during thick coating in winter can be solved by blending a specific metal dryer mixture into the oil-modified alkyd resin paint to achieve well-balanced hardening of the interior and surface of the paint film.

[Structure of the invention]

In the present invention, an epoxy resin undercoat containing an amine curing agent is applied onto a metal base material such as a plant or a ship, and after drying to form an undercoat film, the following metal desiccant mixture is applied to radical A top coat, which is blended in a proportion of 0.3 to 3 parts by weight based on 100 parts by weight of a room-temperature curable solvent-free oil-modified alkyd resin coating composition capable of polymerization and oxidative polymerization, is applied onto the base coat film. A metal desiccant mixture that provides a method for forming an anticorrosion coating film characterized by drying and drying to form a cured coating film: (a) 0.01 to 1 part by weight of a cobalt salt of an organic carboxylic acid; (Metal content) (b) 0.01 to 1 part by weight of lead salt of organic carboxylic acid (Metal content) (C) 0.0001 to 1 part by weight of organic carboxylate of metal selected from manganese, calcium, zirconium, and iron part (metal part).

[Oil-modified alkyd resin] The oil-modified alkyd resin as a component of the oil-modified alkyd resin composition according to the present invention is essentially the same as oil-modified alkyd resins that are conventional or will be provided in the future (α, β
- Also includes those further modified with unsaturated monocarboxylic acids. α
, the method of modification with β-unsaturated monocarboxylic acid is the same as the method of modifying ordinary alkyd resin with fatty acid)
.

Therefore, the polybasic acid components of the alkyd resin include phthalic anhydride, inphthalic acid, tetrahydrophthalic anhydride, adipic acid, sebacic acid, azelaic acid, various conjugated double bond-containing inobrene dispersions, and maleic anhydride.・1 with a side chain obtained by Alder addition reaction
, 2.3.6-tetrahydrophthalic anhydride derivatives such as myrcene maleic anhydride, alloocimene maleic anhydride, ocimene maleic anhydride, 3-(β-methyl-2-butenyl)-5-methyl-1,2,3, 6-titrahydrophthalic acid Hequinahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, aromatic, aliphatic or alicyclic saturation such as trimellitic acid,
Unsaturated polybasic acids are used alone or in combination.

α as part of the saturated polybasic acid within the range where gelation does not occur.
, β-unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. may be substituted. Among these, particularly preferred polybasic acids are phthalic acid and 3-basic acids.
-(β-methyl-2-butenyl)-5-methyl-1,2
, 3,6-tetrahydrophthalic anhydride (hereinafter referred to as MBTH)
P and abbreviation). When MBTHP is used as part of the polybasic acid, it has a remarkable effect on lowering the viscosity of alkyd resins.

Polyhydric alcohol components include ethylene glycol, diethylene glycol, flopylene glycol, cyglobylene glycol, 1.4-7" tanediol, neopentyl glycol, glycerin, pentaerythritol,
Trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)in cyanurate, etc. are used alone or in combination. Generally, dihydric to tetrahydric alcohols having about 2 to 12 carbon atoms are common.

The oil or fatty acid forming the oil-modified alkyd resin includes those having air-drying properties, such as oils and fats such as linseed oil, soybean oil, tall oil, and safflower oil, or fatty acids separated therefrom.

In the present invention, it is preferable to roughly modify the oil-modified alkyd resin consisting of the above three essential components with an α,β-unsaturated monocarboxylic acid. α used here.

β-unsaturated monocarboxylic acids are crotonic acid, sorbic acid or 2-(β-furyl)acrylic acid. Particularly preferred among these is sorbic acid. These α,β-unsaturated monocarboxylic acids introduced into the oil-modified alkyd resin are thought to react in the same way as oil-modified fatty acids and exist as side chains in the alkyd resin, but these acids are When a polymerizable monomer is used as component (2) in the composition of the invention, it undergoes radical copolymerization with the polymerizable monomer and contributes to curing, resulting in a significant effect on improving the hardness and corrosion resistance of the formed film.

Oil-modified alkyd resins are produced from these three essential components or four components by conventional methods, and specifically, for example,
A method in which α, β-unsaturated monocarboxylic acids, fatty acids, polybasic acids, and polyhydric alcohols are simultaneously charged and reacted, or a fatty acid, a polybasic acid, and a polyhydric alcohol are first reacted, and then α, β-unsaturated There is a method of reacting monocarboxylic acids. The latter is preferred from the viewpoint of preventing gelation during production. These components can be subjected to the reaction in the form of their functional derivatives, such as esters such as fats and oils themselves. In addition, when using fats and oils, it is common to perform transesterification by reacting only the polyhydric alcohol with the fats and oils in advance. Furthermore, in any method, it is desirable to add an antigelation agent such as hydroquinone to avoid gelation during the reaction.

The oil-modified alkyd resin used in the present invention has an oil length of 30
-70%, preferably 55-65%. Oil length 30%
If it is less than 70%, it causes a decrease in the water resistance etc. of the resulting coating film, while if it exceeds 70%, undesirable phenomena such as a decrease in the initial drying hardness of the resulting coating film and a decrease in surface smoothness occur. In addition, the oil length in the present invention is the weight percent of the monobasic acid triglyceride derived from the fatty acid separated from the fat or oil in the oil-modified alkyd resin after modification with an α,β-unsaturated monocarboxylic acid. be.

The α,β-unsaturated monocarboxylic acid content in the α,β-unsaturated monocarboxylic acid-modified oil-modified alkyd resin used in the present invention is 0.5 to 30% by weight, preferably 2 to 15% by weight.
%. If the amount is less than 0.5%, no effect of improving the water resistance and hardness of the resulting coating film can be expected, while if it exceeds 30%, gelation will occur during alkyd production, making it difficult to produce.

The oil-modified alkyd resin used in the present invention or α1. β
- The acid value of the unsaturated monocarboxylic acid modified oil-modified alkyd resin is usually about 5 to 40.

[Diluent]

The oil-modified alkyd resin of component (A) has a high viscosity and is difficult to coat as it is. An organic solvent may also be blended.

As the polymerizable monomer, any monomer having at least one radically polymerizable ethylenically unsaturated bond and capable of dissolving the oil-modified alkyd resin in the required yPl+ff1 (details described later) can be used. However, since the resin composition of the present invention is intended to be cured at room temperature or by heating, polymerizable monomers with a somewhat high boiling point of 200°C or higher, such as acrylate or methacrylate with a boiling point of 200°C or higher, are particularly preferred. .

Specific examples of polymerizable monomers that can be used are as follows. These can be used together.

(1) Relatively low boiling point Styrene, methyl methacrylate, divinylbenzene.

(2) High boiling point seven (meth)acrylate carbon number 2
-20, preferably 2-IB monohydric or polyhydric alcohols, preferably monohydric to dihydric alcohols, monoacrylates to monomethacrylates. In this alcohol, the group to which the hydroxyl group is bonded does not necessarily have to be a hydrocarbon, and may have an ether bond, for example.

Some specific examples of such monoacrylates and monomethacrylates are as follows. In the following, the expression "(meth)acrylate" means acrylate and methacrylate.

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethoxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate 1/-toneopentyl glycol mono(meth)acrylate, 3-ptoky7-2-hydroxypropyl (meth)acrylate, 2-hydroxy-1 or 2-phenylethyl (meth)acrylate, polypropylene glycol Monomethacrylate\Glycerin Mono(
meth)acrylate monohalf maleate, diethylene glycol 7-(meth)acrylate, cyclohexyl (
meth)acrylate, benzyl(meth)acrylate,
2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate.

(3) High boiling point di- or tetra(meth)acrylate Alcohol having 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms, having at least two hydroxyl groups, preferably dihydric to tetrahydric alcohol, and acrylic acid or methacrylic acid. There are di-, tri- or tetra-esters of .

In this alcohol, the group to which the hydroxyl group is bonded does not necessarily have to be a hydrocarbon, and may have an ether bond, for example. In addition, for trihydric or higher alcohols,
It is sufficient that at least two of the hydroxyl groups are esterified with acrylic acid or methacrylic acid.

Specific examples of such di-, tri-, and tetraacrylates and methacrylates are as follows.

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin monoacrylate monomethacrylate.

Particularly preferred polymerizable monomers as diluents include tetrahydrofurfuryl acrylate, 2-hydroxypropyl acrylate, 3-butoxy-2-hydroxypropyl acrylate, 1,4-butanediol diacrylate,
These are 1,6-hexanediol diacrylate and trimethylolpropane tri(meth)acrylate.

Examples of non-reactive organic solvents include toluene, xylene, mineral spirit, methyl ethyl ketone, petroleum ether, and ethyl cellosolve.

[Polymerization initiator]

Examples of the polymerization initiator that initiates radical polymerization include methyl ethyl ketone peroxide, benzoyl peroxide, and cyclohexane peroxide.

[Accelerator]

In the present invention, at least three types of metal desiccants, which are accelerators, are used in combination. Namely, (a) a cobalt salt of an organic carboxylic acid, (b) a lead salt of an organic carboxylic acid, and (C) an organic carboxylate of a metal selected from manganese, calcium, zirconium, and iron.

The use of two or more types of metal desiccants in combination is prohibited under the Special Publication Act of 1973.
Publication No. 47726 discloses a technique for preparing a solvent-type oil-modified alkyd resin paint with excellent internal and surface drying properties comparable to lead metal soap using a combination of a zirconium compound having an alkoxy group and a cobalt carboxylate. , US Pat. No. 2,739,902 describes a paint with excellent air-drying properties using a combination of zirconium soap and cobalt soap or manganese soap.

However, even if both techniques are used, when an epoxy resin is used as an undercoat paint, lifting cannot be prevented in winter when an oil-modified alkyd resin topcoat paint is applied directly.

In the present invention, metal soaps of the following components (a), (b), and (C) are used in combination in a specific ratio to provide a coating film with excellent air-drying properties and excellent lifting prevention.

(a) Cobalt salt of organic carboxylic acid 0.01 to 1 part by weight (metal content) (6) Lead salt of organic carboxylic acid 0.01 to 1 part by weight (metal content) (c) Manganese, calcium, zirconium, Organic carboxylic acid salts of metals selected from o, ooi to 1 part by weight (metal content).

[The above blending amount is a blending ratio with respect to 100 parts by weight of the oil-modified alkyd resin. However, if the diluent is a polymerizable monomer, the sum of the oil-modified alkyd resin and the polymerizable monomer is 10
This is the blending ratio relative to 0 parts by weight. ] The cobalt salt of the organic carboxylic acid as the component (a) greatly contributes to the surface drying property of the coating film, and the lead salt of the organic carboxylic acid as the component Φ) greatly contributes to the internal drying property of the coating film. In addition, the organic carboxylate salt of component (c) acts together with components (a) and (b) to contribute to prevention of lifting. However, depending on the type of amino curing agent in the epoxy resin in the undercoat, it may be possible to prevent lifting even in the coldest season by using a combination of cobalt soap (a) and lead soap (b). Component (c), a metal soap, is also used in order to improve the lifting prevention effect.

Component (C) manganese, calcium, iron, or zirconium metal soaps are inferior to the above-mentioned cobalt soaps and lead soaps in terms of drying properties.In particular, when used alone, calcium stone soaps have a drying property. Inferior.

Further, when cobalt soap and manganese soap are used alone, the color difference is larger than that of a coating film obtained from a composition that does not contain these metal soaps.

Note that even if component (c) calcium soap, manganese soap, iron soap, or zirconium soap is used in combination with cobalt soap (a) or lead soap (b), the effect of preventing lifting is small.

Among these components (c), organic carboxylates of calcium are the most effective for internal hardening of paint, so the order of metal reduction potential is higher, that is, Ca.

It is presumed that the j@ of Mn, Zr, Fe, Pb, and Co has the effect of suppressing the formation of ash between the amine curing agent and the polymerization initiator. However, since the top coat cannot be applied unless the surface of the coating film is dry, it is presumed that the use of metal soap in (a) and -) is also essential.

These metal soaps (a), (b), and (c) contain monocarboxylic acids such as naphthenic acid, octenoic acid, isononanoic acid, 2-ethylhequinanoic acid, cycloheptanoic acid, and 2,2-dimethyloctanoic acid. It is obtained by reacting the desired metal in a solvent such as alcohol or acetone.

In addition to (a), (b), and (c), these metal soaps may be used in combination with ironstone and rare earth (lanthanide, cerium, etc.) stone. Particularly preferred blends of metal soaps are as follows (amounts to be blended relative to 100 parts by weight of oil-modified alkyd resin).

Cobalt salt of organic carboxylic acid 0.01 to 0.1 parts by weight (metal content) Lead salt of organic carboxylic acid 0.01 to o, i parts by weight (metal content) Manganese salt of organic carboxylic acid 0.005 to 0. 5 parts by weight (metal content) Calcium salt of organic carboxylic acid 0.01 to 1 part by weight (metal content) Zirconium salt of organic carboxylic acid 0.0003 to 0.003 part by weight (metal content) Iron salt of organic carboxylic acid 0 ~0.001 part by weight (metal content).

These metal soaps are usually dissolved in alcohol, acetone, mineral spirits, etc. before consumption.

〔composition〕

The oil-modified alkyd resin composition used in the present invention includes (A) an oil-modified alkyd resin of 30 to 70% by weight, (B) a diluent for dissolving the above components (70 to 30% by weight), and Ω polymerization initiator described above. 0.01 to 5 weight t% of the sum of ω and ■ components ■ (a) above
, 0.3 to 3 parts by weight based on 100 parts by weight of the accelerator alkyd resin containing the metal soaps of (b) and (c).

The ingredients are 30% of the total amount of ingredients in the oil-modified alkyd resin composition.
~70% by weight, preferably 40-60% by weight.

If it exceeds 70%, the resin composition becomes extremely viscous, making it difficult to prepare or use it, such as coating it. On the other hand, if it is less than 30%, when a polymerizable monomer is used as the component Φ), the corrosion resistance, impact resistance, or bending resistance of the resulting coating film will decrease.

component) is 70 to 30 weight, t%, preferably 60 to 4
It accounts for 0%.

When using a polymerizable monomer as component (6), component (8)
), it is desirable that the amount of di-, tri-, or tetra(meth)acrylate be large in order to obtain a highly hard coating film with excellent corrosion resistance and acid-alkali resistance.

However, in that case, there is a tendency for the flex resistance and impact resistance of the coating film to decrease. Therefore, the content of di- or tetra(meth)acrylate is determined depending on its intended use.

The amount of the combination initiator (C) component is the amount that is usually added to oil-modified alkyd resin paints. The amount of accelerator with zero ingredients is also used in the amount normally used, or slightly more. These (0,
The amount of component 0 is determined taking into consideration the drying properties and anti-lifting properties of the paint.

In addition to these (9) and (0) components, pigments such as titanium oxide, ultramarine, and red, viscosity modifiers such as silicone oil, methyl cellulose, and polyvinyl alcohol, antifoaming agents, etc. are blended. Good too.

[Undercoat paint]

The undercoat paint applied to the base material is an epoxy resin paint containing an amino curing agent.

Examples of epoxy resins include the following.

As a bisphenol type epoxy resin, the product name is Epicoat 82 manufactured by Yuka Shell Epoxy ■, which is generally commercially available.
8, 834, 836, 1001, 1004, 1007; Trade name: Araldite G manufactured by Ciba Geigy ■
Y252, GY250, GY260. Same GY280
, 6071, 6084, 6097: Trade names DER330, 331, 337, 661, 664 manufactured by Dow Chemical; Trade names Epicron 800, 1010, 1000 manufactured by Dainippon Ink and Chemicals. , 301
O: As a phenol novolak type epoxy resin, for example, DEN431, DEN438 manufactured by Dow Chemical Company,
Same 439; Ciba Geigy product name EPN1138:
Product name Epicron N-5 manufactured by Dainippon Ink & Chemicals
65, same N-577; As a polyglycol type epoxy resin, for example, Araldite CT manufactured by Chipa Geigy ■
-5081 Dow Chemical ■Product name DER732,
736, 741; As an ester type epoxy resin, for example, the trade name Epicron 20 manufactured by Dainippon Ink and Chemicals
0, 400, 1400: As epoxidized polybutadiene, trade name BF-1000 manufactured by Nippon Ichika; As epoxidized oil, trade name ADEKA Sizer 〇-180, manufactured by Adeca Argus Chemical ■, 0-130P; etc. can be mentioned.

Furthermore, it should be noted that epoxy compounds and derivatives of the above-mentioned epoxy resins that can be easily inferred from these compositions are also included within the scope of the present invention.

Examples include polyol-type epoxy resins, alicyclic epoxy resins, halogen-containing epoxy resins, silicon-modified epoxy resins, and the like.

The above-mentioned epoxy resins are either liquid or solid at room temperature, and both can be used satisfactorily by adding a solvent that can dissolve them.

Further, there is no problem in using a liquid epoxy resin at room temperature and a solid epoxy resin in combination.

Furthermore, in the present invention, in order to improve the workability, coating performance, and coating condition of the epoxy resin, a monoepoxy resin having one epoxy group in the molecule (an arsenic metal compound) can be used in combination, if necessary.

Examples of the monoepoxy compound include allyl glycidyl ether, 2-ethylhexyl cricidyl ether, methyl glycidyl ether, butyl cricidyl ether,
Examples include phenylglycidyl ether, styrene oxide, cyclohexene oxide, epichlorohydrin, and a compound having one epoxy group obtained by modifying an epoxy resin having two or more epoxy groups in the molecule with a fatty acid or the like.

Furthermore, other resins preferably having a weight of 20 or less can be used in combination with the epoxy resin.

It is not necessary for the concomitant resin to react with the epoxy group in the epoxy resin or the amino group in the curing agent described below, but it may be used to improve the coating workability of the composition, the coating performance, the surface condition of the coating, etc. Can be used in combination with addition. For example, amino resin, phenolic resin, alkyd resin, polyester resin,
Examples include urethanized oil, coal tar, asphalt, xylene resin, polyvinyl formal, and polyvinyl acetal.

On the other hand, examples of the amino curing agent include amino compounds such as amine adduct resins, polyamide resins, and polyamines, which are usually used as curing agents for epoxy resins.

The polyamide resin is a condensation product of dimer acid (general industrial products contain about 3% heptomaric acid, about 85% dimer acid, and about 127o trimer acid) and polyamines such as ethylenediamine, diethylenetriamine, or metaphenylenediamine. It is a thing. For example, commonly available commercially available Fuji Kasei Kogyo product names: Tomide Y-25, Tomide 210, Tomide 215, Tomide 215-X, Tomide 225, Tomide 225.
-x1 2358. 235A, 245, 2400
1 2500: Daiichi General ■Cracked product name Xenamide 20
00, Persamide 115, Persamide 125, Persamide 100, Persamide 14
0, 230, 280, 400, 401, 41
5, DSX-1280; Sanwa Kagaku ■, trade name Sanmide 320, Sanmide 330; Ciel Chemical ■, trade name Ebicure 4255, and the like.

The amine adduct resin is an addition product of the above-mentioned epoxy resin such as a bisphenol type epoxy resin and a polyamine such as ethylenediamine, diethylenetriamine or metaphenylenediamine. For example, Fuji Kasei Kogyo's split product name Tomide 23 is commonly available on the market.
8, Fuji Cure 202, 110; Asahi Denka ■Product name: ADEKA Hardener E) (-531, 101, 532)
, 551, etc.

Furthermore, the amine adducts include butyl glycidyl ether, glycidyl ester of persatic acid, or addition products of bisphenol type epoxy resins and heterocyclic diamines represented by the following formula, for example.

For example, Ajinomoto Iron Split product name Evomate B-002, Evomate B-001, which are generally commercially available. Same C-〇〇2, Same 50
05, 8002, LX-1, RX-2, RX-
3. There is something like N-oat:. These curing agents may be used singly or as a mixture of two or more depending on the purpose.

The curing agent performs a cross-linking reaction with the epoxy resin.
It is necessary that the molecule has at least two or more nitrogen atoms and an active hydrogen bonded thereto. Regarding the curing agent, there are no other restrictions, but the amine value is 5.
It is preferable that it is 0 or more. However, if the amine value of the curing agent becomes extremely high, there will be a restriction that the pot life after mixing with the epoxy resin as the main ingredient will be shortened.

[Painting method]

For painting, apply the above-mentioned epoxy resin undercoat on the base material of plants, ships, bridges, etc., dry it, then apply oil-modified alkyd resin paint 2 to 5 times and repeat drying. , obtain a coating film of desired thickness.

The coating is performed by brush coating, air spray coating, airless coating, or the like so that the dry coating film has a thickness of 30 to 500 microns.

On top of this oil-modified alkyd resin coating, another paint, such as a polyester paint, an alkyd paint, or a vinyl chloride paint, may be further applied.

The present invention will be explained below with reference to Examples.

All "parts" in the following Examples and Comparative Examples mean parts by weight.

[Production of oil-modified alkyd resin]

Production Example-1 62.0 parts of dehydrated castor oil fatty acid, 12.6 parts of phthalic anhydride, MBTHP 9.94, glycerin 1. 5 parts and 17.8 parts of pentaerythritol, the hydroquinone component concentration was 3.0%, and the oil length was 64.
An 8% oil-modified alkyd resin (resin-human) was obtained.

Production example-2 Dehydrated castor oil fatty acid 53-48, phthalic anhydride 13.5
Miyako, MBTHpl 0.7i, Pentaerythritol 2
The reaction was carried out in exactly the same manner as in Production Example-1, except that 1.7 parts of sorbic acid and 7 g of sorbic acid xo were used, and the final acid value was 35. Sorbic acid component concentration 1i was 10.7% and oil length was 55.8%.
An oil-modified alkyd resin (resin-B) was obtained.

Production example-3 52.9 parts of soybean oil fatty acid, 4.9 parts of phthalic anhydride, M
The reaction was carried out in exactly the same manner as in Production Example-1 except that 7 parts of BTHPll, 5.5 parts of glycerin, 15.1 parts of pentaerythritol, and 7.1 parts of sorbic acid were used to obtain a sorbic acid component concentration of 7.1%. An oil-modified alkyd resin (resin-C) with an oil length of 55.3% was obtained.

Production example-4 Dehydrated castor oil fatty acid 56.5 parts, phthalic anhydride 15.0
parts, 1.9 parts of MBTHPi, 6.7 parts of glycerin, 13.5 parts of pentaerythritol, and 3.5 parts of crotonic acid.
The reaction was carried out in exactly the same manner as in Fi production example-1 except that 10% of the crotonic acid component was used to obtain an oil-modified alkyd resin (resin-D) having a crotonic acid component concentration of 3.5% and an oil length of 59.0%.

Production Example-5 Dehydrated castor oil fatty acid 5466 parts, 7-talic anhydride 15.1 parts
%, MBTHPl 2.0 parts, glycerin 7.7 parts, pentaerythritol 12.1 parts% and 2-(β-furyl)acrylic acid 5.4 parts, but the reaction was carried out in exactly the same manner as in Production Example-1. 2-(β-furyl)acrylic #oil-modified alkyd resin with component concentration 5.4% and oil length 57.1% (
Resin-E) was obtained.

Production Example-6 60.0 parts of dehydrated castor oil fatty acid, 26.9 parts of phthalic anhydride, 14.8 parts of glycerin, and pentane were placed in a reactor equipped with a stirrer, thermometer, cooler, water separator, and nitrogen inlet tube. After charging 5.4 parts of erythritol and further adding 4 parts of xylene, the reaction was carried out at 220° C. in a nitrogen stream until the acid value reached 20 or less. Water, xylene, etc. were removed to obtain a yellow-brown dehydrated castor oil fatty acid-modified alkyd resin (resin-F) with an oil length of 62.8%.

Preparation of epoxy resin base coating Bottom @Paint A.

Bisphenol type epoxy resin (oiled shell epoxy)
Product name Epicoat 1001, Epoxy 1450-5
00) Total ethylene glycol monobutyl ether 100
A resin solution whose nonvolatile content was adjusted to 50% was obtained.

The above resin solution was processed with 50 parts of red iron oxide, 100 parts of talc, 50 parts of precipitated barium sulfate, and 100 parts of ethylene glycol monobutyl ether and kneaded in an o-y- to obtain a main ingredient.

On the other hand, a polyamide resin (product name: Tomide 225, manufactured by Fuji Kasei Kogyo ■, Aban number 300±20) was dissolved in ethylene glycol monobutyl ether and the nonvolatile content was adjusted to 50% to prepare a curing agent.

The mixing ratio of main agent/curing agent is lOO/15 (weight ratio).

Primer paint B.

The base agent used was the same as the base agent for undercoat paint A.

On the other hand, a polyamide resin [trade name Persamide 115 manufactured by Daiichi Vineral ■, amine value 230-246] was dissolved in ethylene glycol monobutyl ether to give a non-volatile content of 50%.
It was used as a curing agent.

The mixing ratio of main agent/curing agent was 100,720 (weight ratio).

Undercoat paint C1 The base agent used was the same as the base agent for undercoat paint A.

On the other hand, 30 parts of amine adduct resin [Fuji Kasei Kogyo Co., Ltd., product name: Fuji Cure 202, activated water cable [1120]], polyamide resin [Fuji Kasei Kogyo Co., Ltd., product name: Tomide 22]
5. Amine value: 300±20) 70 parts of ethylene glycol monobutyl ether Kl was added thereto to adjust the non-volatile content to 50% to prepare a curing agent.

The mixing ratio of main agent/curing agent was 100/15 (weight ratio).

[Preparation of resin composition and performance evaluation as paint]

Examples 1 to 5, Comparative Examples 1 to 13 Polymerizable monomers of a mixture of 55 parts of oil-modified alkyd resin-A obtained in Production Example 1 and 10 parts of hydroxypropyl methacrylate and 35 parts of 1,4-butanediol diacrylate Dissolved in the body.

Based on the weight of this solution *
, calcium naphthenate (calcium content 3%), iron naphthenate (iron content 5%), zirconium naphthenate (zirconium content 4%), and cyclohexanone peroxide were blended to prepare an oil-modified alkyd resin top coating.

Polished mild steel plate with primer paint A (50m x 150m.

It was applied to a 50 micron film (with a thickness of 0.3 m and polished with a ◆320 polishing cloth) and then dried in an air bath at 5° C. for 2 days.

On the obtained undercoat # Drying time was measured. The results are shown in the same table.

On the other hand, a top coat was applied and dried at 5℃ for 2 days.
A top coating having the same composition as shown in Table 1 was applied on top of the 0 micron film, and dried at 5°C for 2 days. Fallen peta.

The results are shown in the same table.

(Left below) Example 6 Same as Example 1 except that the undercoat was changed as shown in Table 2.
Using the same ICL machine, paints prepared using the metal soap shown in the table were examined for drying time to the touch, gloss of the paint film, and presence or absence of lifting.

The results are shown in the same table.

The abbreviations in the table are as follows.

HPA: Hydroxyprobyl methacrylate BDDA:
1.4-Butanediol diacrylate Co: Cobalt naphthenate Mn: Manganese naphthenate Pb: Lead naphthenate zr: Zirconium naphthenate Ca: Calcium naphthenate Mix: Same metal soap mixture as in Example 1 (hereinafter referred to as the margin), page 1) Kazuyoshi Akira Uchimura of 12 Daito-cho, Tsurumi-ku, Yokohama Minoru Shinohara 100 of Daito-cho 12, Tsurumi-ku, Yokohama Osamu Ogawa 1-1 of Daito-cho 12, Tsurumi-ku, Yokohama Dainippon Toyo Co., Ltd. Technical Headquarters 1 Dainippon Toyo Co., Ltd. Technical Headquarters Procedural Amendment (Voluntary) January 28, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of Case 1980 Patent M No. 2291962, Name of the invention Method 3 of forming an anticorrosive coating film, relationship with the amended case Patent applicant address 25-5 Toranomon-chome, Minato-ku, Tokyo Name Mitsubishi Yuka Fine Co., Ltd. Address 6 Nishikujo, Konohana-ku, Osaka Chome 1-124 Name (
332) Dainippon Toyo Co., Ltd. Representative Toshiyuki Nakamura 4, Agent address: 2-5-2-5 Marunouchi, Chiyoda-ku, Tokyo, Subject of amendment - Detailed explanation of the invention in the specification column 6, Contents of amendment Patent application Amendment (1) of No. 59-229196: The descriptions shown in the table below in the Detailed Description of the Invention column of the specification (left column) are amended as in the right column.

18□, 17I amine curing agent: amine curing agent
i'30.8: Oil-modified alkyd resin Oil-modified alkyd resin 1j34:12. Wall thickness; film thickness
;: 3□: 6 -:
. , o3 1(2), page 19, line 8, delete "iron soap".

(3) The entire text on pages 38, 39, and 40 will be deleted and replaced with the following sentences.

"Example 6 The drying time to the touch, the gloss and lift of the paint film, The presence or absence of

The results are shown in the same table.

(The following is a blank space)" Example 7 In Example 1, the oil-modified alkyd resin, polymerizable monomer, type of polymerization initiator,
Coating was performed and evaluated in the same manner except that the amount was changed as shown in Table 3.

The results are shown in the same table.

Table-3 7-'B(ss):101'3510.18771-
1 t 116.2 Innocent s', C(“so+20,
3sn l-,'l, 15.1 //91D (551t
o□35' tt knee 11, 15.0',
〃* CI-IN Cyclohexanone peroxide MEK Methyl ethyl ketone peroxide 1 (P
A Hydroxypropyl methacrylate BDDA
1,4-butanediol diolite** indicates metal content

Claims (1)

[Claims] 1) After applying an epoxy resin undercoat containing an amino curing agent onto a substrate and drying it to form an undercoat film, the following metal drying agent mixture undergoes radical polymerization. and a top coat, which is blended in a proportion of 0.3 to 3 parts by weight per 100 parts by weight of an oxidatively polymerizable room-temperature curable solvent-free oil-modified alkyd resin coating composition, is applied onto the base coat film. A method for forming an anticorrosion coating film characterized by drying to form a cured coating film Metal drying agent mixture: (a) 0.01 to 1 part by weight of cobalt salt of organic carboxylic acid (metal content) (b) 0.01 to 1 part by weight (metal content) of a lead salt of an organic carboxylic acid (c) 0.0001 to 1 part by weight (metal content) of an organic carboxylate salt of a metal selected from manganese, calcium, zirconium, and iron. 2) The oil-modified alkyd resin coating composition is modified with (2) an α,β-unsaturated monocarboxylic acid selected from sorbic acid, crotonic acid and 2-(β-furyl)acrylic acid with an oil length of 30 to 70. % of oil-modified alkyd resin (however, the α,β-unsaturated monocarboxylic acid content is 0.5 to 30% by weight) 30 to 70% by weight (B) Component Polymerizable monomer that dissolves the above (A) body 70~3
0% by weight (C) Radical polymerization initiator: 0.01 to 5% by weight of the sum of components (A) and (B). Method described.