KR19980042879A - Bittar-type epoxy resin coating composition, coating method of ship shell and coated ship - Google Patents

Abstract

The bittar type epoxy resin coating composition of this invention contains the hardening | curing agent containing (a) bisphenol epoxy resin, (b) vinyl chloride copolymer, and (c) polyamide or its modified substance. The vinyl chloride copolymer (b) is preferably a vinyl chloride / alkyl vinyl ether copolymer. The medium anticorrosive coating film of the present invention is a film formed from the above-mentioned coating composition. The paint composition shows excellent performance as a heavy coating composition available for all parts of the ship, such as shells, exposed decks, superstructures, holds and ballast tanks. If the surface of the medium anticorrosive coating (coating of the coating composition) is applied with an inorganic tin-based hydrolytic antifouling paint or various upper coatings, excellent adhesion between the medium anticorrosive coating and other films can be provided. The coating method of the ship shell according to the present invention is applied to the bottom of the ship (i) or the bottom of the ship and the repair of the ship (ii) as a primer with a non-tar epoxy resin medium coating composition to form a primer coating film, and then And applying the surface of the primer coating film with an inorganic tin-based hydrolytic antifouling paint. The above-mentioned bittar type epoxy resin coating composition is advantageous as a medium anticorrosive coating composition. In this coating method, the film which has the outstanding anticorrosive property, weather resistance, and antifouling property can be formed using the kind of paint with few types. Therefore, the method can reduce the painting time, reduce the cost of storing the paint, and is advantageous for the sanitary and environmental protection of the painter. The coated vessel of the present invention comprises a non-tar epoxy resin medium coating coat primer coat formed on the bottom of the ship (i) or the bottom and the repair of the ship (ii) and formed on the primer coating. Antifouling coatings.

Description

Bittar type epoxy resin coating composition, coating method of ship shell and painted vessel

The present invention relates to a bittar-type epoxy resin coating composition, a heavy-duty coating film formed from the composition, a coating method of a ship shell and a painted vessel. In particular, the present invention exhibits excellent performance as a medium anticorrosive coating composition that can be applied to all parts of the ship, such as ship shell, exposed deck, superstructure, hold and ballast tank, inorganic tin-based hydrolytic pollution The present invention relates to a non-tar epoxy resin coating composition capable of forming a coating film having excellent adhesive strength on a prophylactic coating film or various upper coating films of various kinds formed thereon. The present invention also relates to a medium anticorrosive coating film formed from the coating composition. Furthermore, the present invention relates to a coating method of the outer shell of the ship, by which the coating film having excellent corrosion resistance, weather resistance and anti-fouling properties can be formed by using a very small type of paint, thereby reducing the coating time and paint storage The cost can be reduced and it is beneficial to the sanitary and environmental protection of painter. The invention also relates to ships painted in this way.

For various parts of the ship, such as ship shells, exposed deck sections, superstructures, hold sections and ballast tank sections, other heavy coating compositions have been used so far.

In this part of the ship, for example, the ship's shell is always located between the bottom (including fresh water and sea water), the submerged topside and the boot topping and the outer surface. It can be roughly divided into subdivisions, which are repeatedly submerged in water and exposed to the atmosphere. When painting the ship's shell, the exterior paint is required to have weather resistance because the exterior is exposed to strong sunlight and rough waves, and the bottom paint is required to have antifouling properties because the bottom is always locked. Bouillon coatings are required to have weather resistance, water resistance and sometimes antifouling properties since the repair portion is submerged in rough waves and repeatedly exposed to the atmosphere.

Therefore, in order to coat the parts with a paint that satisfies the above requirements, at present, a plurality of exclusive primers are prepared in consideration of the adhesive strength, thereby ensuring the adhesive strength and corrosion resistance.

Until now, the bottom part and sometimes the repair part have been thickly coated with tar type epoxy resin medium anticorrosive coating composition which is excellent in anticorrosion. However, this type of paint is resistant to corrosion, welding heat or cutting heat after coating because tar is carcinogenic or tar is black. There is a problem that it is difficult to visually determine the burnout and coating state caused by the eye.

In addition, tar-containing paints may tar the vessel's aesthetic appearance by bleeding into the upper coating layer formed on the coating or adversely affect various functions such as anti-fouling and weather resistance.

As primers for the outer and sometimes repair parts of ship shells, non-tar-type primers are generally used to avoid the tar bleeding mentioned above. Therefore, when using the tar type epoxy intermediate anticorrosive coating composition excellent in anticorrosive property as a primary road for a ship bottom or a ship bottom and a repair part, much care is needed. For example, tar- and non-tar-type primers should coat these primers while protecting the boundaries (eg, attaching sheets or tapes to protect the unpainted areas). Overlapping parts (where the different paints overlap) must be handled with care during the painting process. In addition, when other paints are used, the painting machine needs to be sufficiently cleaned, which requires complicated processes and the use of diluents.

In addition, in the conventional coating method, when applying the surface of the coating film formed of the tar-type epoxy heavy-duty coating composition with the inorganic tin hydrolyzable antifouling paint, the adhesive strength between the coating layers is low, so that the vinyl or tar vinyl type is preferentially applied. It is necessary to coat the binder paint on the tar-type epoxy intermediate coating film and to apply the non-organic hydrolytic antifouling paint to the binder paint. If the upper coating is to be applied to the tar type epoxy intermediate coating, the coating of the upper coating is performed at a time interval. In the case of a tar epoxy curing coating composition, the spacing is relatively short, which requires a complicated process and complicated construction management.

In the conventional coating method, the heavy-duty coating composition used for the part other than the submerged part of the ship shell and the exposed signboard part is different as described above, and a dedicated upper paint and a dedicated binder paint are used for each part. In addition, according to the various demands of consumers, a very large number of paints must be prepared and construction management is required. Therefore, the cost of paint storage and paint transport is high. Moreover, due to the complicated painting process, coating takes a long time and the process management becomes complicated.

Thus, a single type of primer coating is formed on all parts of the ship, such as ship shells (including bottom, outer and repair), exposed signboard, superstructure, hold and ballast tanks, When the primer coating film is the same as the inorganic tin hydrolyzable antifouling paint, it can form an upper coating film with excellent anticorrosion and adhesive strength and can reduce the coating time. Is currently required.

In addition, it is possible to apply the outer shell of the ship in a specific order with a small amount of paint to form an excellent anti-pollution coating, reduce the painting time and reduce the cost of storing the paint, and lathe for the sanitary and environmental protection of the painter There is a need for the development of a method of painting the shell.

The present invention seeks to solve the problems associated with the prior art described above, and an object of the present invention is to provide a heavy-duty coating composition that can be used as a primer that can be applied to all parts of the ship, such as the ship shell and exposed deck portion. Thus, the use of a binder paint can be omitted when using an inorganic tin-based hydrolyzable antifouling paint, and ships various functions such as corrosion resistance, weather resistance, water resistance, and antifouling properties that are equivalent to or higher than those of the conventional tar type epoxy heavy anticorrosive coating composition. The present invention provides a non-tartar type epoxy resin coating composition which is applied to an outer plate or other vessel part, which is advantageous for streamlining the painting process, reducing the cost of storing the paint, and protecting the sanitary and environmental protection of the painter.

Another object of the present invention is to provide a medium anticorrosive coating film formed from the coating composition.

Another object of the present invention is to use only one type of specific marine shell paint as a primer and apply it with very few kinds of paint without the use of any other binder paints, so that the ship shell has the necessary properties such as corrosion resistance, weather resistance, water resistance and anti-pollution. It can provide performance, streamline the painting process, reduce paint storage costs, and provide a method of painting ship shells that is beneficial to the painter's hygiene and environmental protection.

Another object of the present invention is to provide a vessel painted by the method.

The nontartar type epoxy resin coating composition according to the present invention is:

(a) a bisphenol epoxy resin (preferably a bisphenol epoxy resin having an epoxy equivalent of 100 to 500),

(b) vinyl chloride copolymer, and

(c) a curing agent comprising polyamide or modified product thereof.

Furthermore, the coating composition of the present invention preferably further contains aluminum powder (d) in the components (a), (b) and (c). The tricresyl phosphate is contained in the coating composition of this invention. In the present invention, the vinyl chloride copolymer is preferably a vinyl chloride / alkyl vinyl ether copolymer.

The bittar type epoxy resin coating composition is used as a medium anticorrosive coating composition.

The medium anticorrosive coating film according to the present invention is formed from a bittar type epoxy resin coating composition.

According to the non-tar epoxy resin coating composition of the present invention, the medium anticorrosive coating composition for various ship parts, such as the ship shell and exposed deck, can be unified into one type of medium anticorrosive coating composition, and the inorganic tin-based water The use of binder paints can be omitted for future use of degradable antifouling paints. Moreover, the ship shell and other parts of the ship can be given various functions equivalent to or more than the conventional tar type epoxy resin anticorrosive coating composition, such as anticorrosion, weather resistance, water resistance and antifouling.

In addition, even when an upper coating material such as an inorganic tin-based hydrolytic antifouling paint was applied to the coating film of the non-tartar type epoxy resin coating composition at intervals without using a binder, excellent interlayer adhesion strength was obtained. This is that the paint composition of the present invention can contribute to the rationalization of the painting process, the rationalization of the ship-building process and the reduction of the paint storage cost. Moreover, the non-tar-type epoxy resin coating composition is advantageous for the sanitary and environmental protection of the painter.

The coating method of the ship shell according to the present invention is:

(i) the bottom of the ship or (ii) the bottom of the ship and the repair of the ship are applied with a non-tar epoxy resin anticorrosive coating composition as a primer to form a primary coating film; And

And further applying the surface of the primer coating film with an inorganic tin-based hydrolytic antifouling paint.

In the present invention,

The entire outer shell of the vessel including the bottom, the repair and the outer surface is applied with a non-tar epoxy resin anticorrosive coating composition as a primer to form a primer coating film; And

It is possible to further apply the surface of the primer coating film prepared on the (i) bottom part or (ii) bottom part and the repair part of the primer-treated outer plate with an inorganic tin-based hydrolytic antifouling paint.

In the present invention,

The entire outer shell of the vessel including the bottom, the repair and the outer surface is applied with a non-tar epoxy resin anticorrosive coating composition as a primer to form a primer coating film; And

The surface of the primer coating film prepared on the (i) bottom part or (ii) bottom part and the repair part of the primer-treated outer plate is further coated with an inorganic tin hydrolyzable antifouling paint, and the surface of the primer coating film formed on the outer part part. Is applied to the outer surface upper paint;

And if necessary;

It is also possible to apply the repair part further with the repair top paint.

The painted vessel according to the invention is:

(i) the bottom of the ship or (ii) the non-tar epoxy mid-type primer coating film formed on the bottom and repair of the ship, and

And an inorganic tin hydrolyzable antifouling coating film formed on the primer coating film.

The painted vessel of the present invention is:

Bittar type epoxy resin medium anticorrosive primer coating film formed on the entire outer plate of ship including bottom, repair and outer part, and

An inorganic tin-based hydrolyzable antifouling coating film formed on the (i) bottom portion or (ii) the bottom portion and the repair portion outside the entire primer coating film.

The painted vessel of the present invention is:

Bittar type epoxy resin medium anticorrosive primer coating film formed on the entire outer plate of ship including bottom, repair and outer part

(I) the bottom of the entire primer coating or (ii) the inorganic tin-based hydrolytic antifouling coating film formed on the primer coating prepared on the bottom and the repair,

An upper outer coating film formed on the primer coating film prepared on the outer surface,

And if necessary,

The repair part may include an upper coating film formed on the repair part.

In any of the above-mentioned coating methods of the present invention and a painted vessel, it is preferable that the non-tar epoxy epoxy anticorrosive coating composition (primer) or the primer coating film obtained by applying and curing the composition further comprises a thermoplastic resin.

The thermoplastic resin is preferably at least one resin selected from chlorinated polyolefins, acrylic resins, vinyl acetate resins, styrene resins and vinyl chloride-based resins. The vinyl chloride resin is preferably a vinyl chloride / vinyl alkyl ether copolymer, more preferably a vinyl chloride / vinyl isobutyl ether copolymer.

In this invention, it is preferable that the coating film obtained by apply | coating and hardening a non-tartar type epoxy resin medium anticorrosive coating composition or the said coating material contains an aluminum powder.

In this invention, it is preferable that the coating film obtained by apply | coating and hardening an outer surface upper paint or the said upper paint contains a urethane paint, an epoxy paint, an acrylic paint, or a chlorinated polyolefin paint (chlorinated rubber paint); In addition, it is preferable that the upper coating material of the repair portion or the coating film obtained by applying and curing the paint includes a urethane paint, an epoxy paint, an acrylic paint, a chlorinated polyolefin paint (chlorinated rubber paint), an inorganic tin antifouling paint, or a mixture of these paints. Do.

In the present invention, the inorganic tin-based hydrolyzable antifouling paint or the coating film obtained by applying and curing the paint contains 20 to 65% by weight in component units derived from trialkylsilyl esters of polymerizable unsaturated carboxylic acids. It is preferred to include trialkylsilyl ester copolymers having a molecular weight of 1000 to 50,000.

In the present invention, it is preferable that the organic tin-based hydrolytic antifouling paint or the coating film obtained by applying and curing the paint contains a vinyl resin in which an organic acid is connected to at least one or more side chain ends by metal ester bonds.

According to the coating method of the ship shell of this invention, the coating film excellent in anticorrosiveness, weather resistance, and pollution prevention can be formed by a small kind of paint. Therefore, the method reduces paint time, saves paint storage cost, and is advantageous for painter's hygiene and environmental protection.

Vessels painted according to the invention can be produced by carrying out hygienic painting operations for a short time using very few kinds of paints and have good corrosion resistance, weather resistance and antifouling properties.

The non-tartar type epoxy resin coating composition, the coating film formed from the composition, the coating method of the ship shell and the painted vessel according to the present invention will be described in more detail below.

Bittar type epoxy resin coating composition

The non-tartar type epoxy resin coating composition of the present invention is:

(a) bisphenol epoxy resins,

(b) vinyl chloride copolymer, and

(c) a curing agent comprising polyamide or modified product thereof.

(a) bisphenol epoxy resin

The epoxy resin used in the present invention is preferably a bisphenol epoxy resin having an epoxy equivalent of 160 to 500, more preferably 160 to 300. The epoxy resin is usually solid in the liquid phase. It is preferable that the epoxy equivalent of the bisphenol epoxy resin used for the coating composition of this invention exists in the said range from the viewpoint of the adhesive strength of a coating composition, and the workability of a coating process.

Since the coating composition of this invention contains bisphenol epoxy resin among various epoxy resins, the coating film formed from the composition is strong and flexible, and shows the outstanding adhesive strength.

Examples of bisphenol epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, dimer acid-modified epoxy resins, polysulfide-modified epoxy resins, and hydrogenated products of such bisphenol epoxy resins.

Examples of bisphenol A type epoxy resins include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and hydrogenation Diglycityl ethers of bisphenol A type, such as bisphenol A propylene oxide diglycidyl ether. Examples of bisphenol F type epoxy resins include bisphenol F diglycidyl ethers such as bisphenol F diglycidyl ether.

Of these, bisphenol A type epoxy resins are preferred.

Examples of the epoxy resin in the liquid state at room temperature include, for example, Epikote 828 (available from Cell Co., Ltd., epoxy equivalent: 180-190, viscosity: 12,000-15,000 cPs / 25 ° C), Efototo YDF-170 ( Epotohto YDF-170; available from Toto Kasei Co., Ltd., Epoxy equivalent: 160-180, Viscosity: 2,000-5,000 cPs / 25 ° C) and Prep 60 (available from Torep Thiocol High School, Epoxy equivalent: approx. 280, viscosity: about 17,000 cPs / 25 ° C.).

Examples of epoxy resins that are semi-solid at room temperature are the trade names Epikote 834 (available from Cell Co., Epoxy equivalent: 230-270) and Epotohto YD 134 (Toto Kasei Co., Ltd.). Possible epoxy equivalents: 230 to 270). Examples of epoxy resins that are solid at room temperature include Epikote 1001 (available from Cell Co., Epoxy equivalent: 450-500) under the trade name.

In addition to bisphenol epoxy resins (a) having an epoxy equivalent of 160 to 500, other epoxy resins may be used in the present invention. For example, an epoxy resin having an epoxy equivalent of 500 or more and a bisphenol epoxy resin and other epoxy resins do not violate the object of the present invention, for example, 60 per 100 parts by weight of the bisphenol epoxy resin (a). It may be used in an amount that does not exceed parts by weight.

Epoxy resins whose epoxy equivalent is not 160 to 500 include, for example, epoxy resins of Epotohto YD-172 (available from Toto Kasei Co., Ltd., epoxy equivalent: 600 to 700) under the trade name. Examples of non-bisphenol type epoxy resins include cycloaliphatic, acyclic aliphatic and epoxidized emulsifying systems.

(b) vinyl chloride copolymer

Examples of the vinyl chloride copolymer (b) include vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl propionate copolymer, vinyl chloride / alkyl vinyl ether copolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / di Ethyl maleate copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / maleic anhydride copolymer, vinyl chloride / alkyl (meth) acrylate copolymer (number of carbo atoms of alkyl group: about 1 to 5), vinyl chloride / styrene Copolymers, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / vinyl stearate copolymer, vinyl chloride / maleic acid (or maleic acid ester) copolymer and vinyl chloride / aliphatic vinyl copolymer.

Graft modifications of polyvinyl chloride obtained by grafting polyvinyl chloride with other monomers other than vinyl chloride and copolymers obtained by graft modification of polymers other than polyvinyl chloride with polyvinyl chloride monomers Denaturates are available.

Examples of other monomers include (meth) acrylic acid alkyl esters (about 1-5 carbon atoms in alkyl groups), styrene, acrylonitrile, diethyl maleate, olefins (eg, monomers for forming vinyl chloride copolymers) Ethylene, propylene), maleic anhydride, vinylidene chloride, stearic acid, maleic acid, maleic acid esters and aliphatic vinyl.

Among the vinyl chloride copolymers (b), vinyl chloride / alkyl vinyl ether copolymers are preferred because they are excellent in affinity with bisphenol epoxy resins (a) and have excellent overcoatability and corrosion resistance. .

Examples of preferred vinyl chloride / alkyl vinyl ether copolymers used in the present invention include carbon chloride / isobutyl vinyl ether copolymers, vinyl chloride / isopropyl vinyl ether copolymers and vinyl chloride / ethyl vinyl ether copolymers. Copolymers of vinyl chloride and alkyl vinyl ethers containing alkyl groups of 1 to 10, preferably 2 to 5;

The vinyl chloride copolymer (b) is required to have a weight-average molecular weight (Mw) of usually 10,000 to 100,000, preferably 20,000 to 50,000, particularly preferably 22,000 to 40,000. If the weight-average molecular weight is within this range, the affinity of the copolymer for epoxy resin is improved.

Among the vinyl chloride / alkyl vinyl ether copolymers, vinyl chloride / isobutyl vinyl ether copolymers include, for example, Laroflex LR8829, Laroflex MP25, Laroflex MP35, and Laroflex MP45 (all are trademarks of BASF Corporation). Available from).

These vinyl chloride copolymers may be used alone or in combination of two or more thereof.

The vinyl chloride copolymer (b) may be used in an amount of usually 5 to 90 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the bisphenol epoxy resin (a), which is a component of the bittar type epoxy resin coating composition. . When the vinyl chloride copolymer (b) is included in this amount in the coating composition, the copolymer exhibits good affinity for the bisphenol epoxy resin (a) and the composition has good anticorrosion and topological properties. It is preferable that the compounding ratio of the vinyl chloride copolymer (b) is within the above range in consideration of both the anticorrosive properties of the resulting coating film and the top coat with the upper paint.

Together with the vinyl chloride copolymer (b) which is a thermoplastic resin, other thermoplastic resins other than the vinyl chloride copolymer may be included in the coating composition of the present invention without departing from the object of the present invention. In the non-tar epoxy resin coating composition, the thermoplastic resin other than the vinyl chloride copolymer (b) has a total amount of the thermoplastic resin component including the vinyl chloride copolymer (b) based on 100 parts by weight of the bisphenol epoxy resin (a). 5 to 90 parts by weight, preferably 7 to 50 parts by weight, and more preferably 10 to 30 parts by weight.

The thermoplastic resin (rubber) comprising the vinyl chloride copolymer (b) acts as an emollient to relieve internal tension when the non-tar-type epoxy resin coating composition (epoxy paint, epoxy heavy-duty paint composition) is cured, thereby providing a substrate or undercoat. It is possible to improve the adhesive strength between the layer and the epoxy layer formed from the epoxy paint. The thermoplastic resin (rubber) is solvent soluble and can be dissolved in the solvent contained in the upper paint, thereby improving the adhesion strength of the epoxy layer to the upper paint or relaxing the restriction of the paint gap of the epoxy paint (i.e. extending the coating interval). Increase the type of top coating that can be applied to the epoxy film.

Examples of the thermoplastic resin (rubber) other than the vinyl chloride copolymer (b) include chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; Acrylic resins such as methyl (meth) acrylate copolymers, propyl (meth) acrylate copolymers, butyl (meth) acrylate copolymers and cyclohexyl (meth) acrylate copolymers; Styrene resins; Aromatic petroleum resins; Aliphatic petroleum resins; Urea-aldehyde condensed resins; Ketone resins; Coumarone-indene resin; And pentadiene polymers.

These thermoplastic resins (rubbers) may be used alone or in combination of two or more.

(c) curing agents comprising polyamides or modified products thereof

As the curing agent (c) for the bisphenol epoxy resin (a), polyamide or a modified product thereof is used. Since the non-tar epoxy coating composition including the curing agent (c) can be cured at room temperature, the composition is easy to use when performing painting work at room temperature in general, that is, when painting the ship shell.

It is preferred that the polyamide and its modified product usually have an amine value of 50 to 1,000, preferably 80 to 500. When the amine value of the curing agent is within this range, there is a tendency that the balance between dryness and adhesive strength is improved. Curing agents are generally liquid to solid.

Examples of polyamide are under the trade name Luckamide N-153 (available from Dainippon Ink Chemical Co., Ltd., amine number: 80-120), Luckamide TD-966 (available from Dainippon Ink Chemical Co., Ltd.) Amine number: 150-190) and sunmid 315 (available from Sangwa Chemical Industry Co., Ltd., amine number: 280-340).

Examples of modified products of polyamides include epoxy impregnated by adding an epoxy compound to polyamides such as PA-23 (trade name, available from Odake Chemical Co., Ltd., amine number: 80-150) and adeka curing agent EH-350. Mannich modified products of modified polyamides (trade name, available from Asahi Denka Kogyo, Amine Number: 320-380).

It is preferable that the adduct of an epoxy compound is used for a polyamide and its modified substance.

Polyamide and its modified product are preferably used alone or in combination of two or more thereof.

In the present invention, the polyamide or the modified product thereof has an equivalent ratio between the epoxy of the bisphenol epoxy resin (a) and the amine of the curing agent in the bittar-type epoxy resin coating composition, usually from 1: 0.35 (epoxy component: amine component) to 1: 0.9, preferably in an amount of from 1: 0.4 to 1: 0.8. When polyamide or its modified material is used in this amount, the coating film formed from the composition has excellent dryness, anticorrosion and topological properties. In other words, polyamide or its modified substance is usually used in an amount of 10 to 80 parts by weight, preferably 20 to 70 parts by weight, relative to 100 parts by weight of the bisphenol epoxy resin (a) in the bittar-type epoxy resin coating composition.

In the present invention, a polyamide and a modified agent for an epoxy resin other than its modified product may be included within a range that does not impair the object of the present invention.

The curing agent is not particularly limited as long as it reacts with the epoxy resin to be cured. For example, other amine type curing agents, carboxylic acid type curing agents, acid anhydride type curing agents, and silanol type curing agents other than polyamide and other modified substances may be used. The amine type curing agent is preferably a liquid to solid phase curing agent having an amine number of 50 to 1,000, preferably 80 to 500.

Examples of amine type curing agents for epoxy resins include aliphatic amines such as polyalkylenepolyamines, aromatic amines and alicyclic amines. Epoxy adducts, Mannich modifications and carboxylic acid modifications in which epoxy compounds are added to these amines can also be used.

Ketamine type curing agents obtained by modifying these amine compounds into ketones may also be used.

Examples of the amine compound optionally used in the present invention include modified alicyclic polyamines of the ketimine type such as an anchoramine MCA (trade name, Anchor Chemical Co., Amine: 250-350); Modified phenol amines such as Cadelite 541LV (trade name, available from Cadelite Co., Ltd., Amine Value: 260-350); And modified aromatic polyamines such as Adeka Curing Agent EH101 (trade name, available from Asahi Denka Kogyo, Amine Number: 400-500).

These amine compounds may be used alone or in combination of two or more.

The amine compound is usually 10 to 80 parts by weight, preferably 100 parts by weight of polyamide or its modified product (c) and the amine compound to 100 parts by weight of the bisphenol epoxy resin (a) in the non-tar epoxy resin coating composition. Is used to 20 to 70 parts by weight. In other words, the amine compound is used such that the equivalent ratio between the epoxy of the resin (a) and the amine of the curing agent is usually 1: 0.35 (epoxy equivalent: amine equivalent) to 1: 0.9, preferably 1: 0.4 to 1: 0.8. do.

Other additives

In the non-tar epoxy resin coating composition (medium anticorrosive coating composition) of the present invention, a plasticizer, an extender pigment, a coloring pigment, a rust proof pigment, a solvent, a curing accelerator, an anti-sagging agent and an antisettling agent Various additives, such as anti-settling agents, can be included in addition to the above ingredients.

It is preferable that the bittar type epoxy resin coating composition of this invention contains aluminum powder as a pigment component. Examples of the aluminum powder include leaf form and non leaf form aluminum powder having an average particle diameter of 1 to 100 μm.

When the aluminum powder is added to the coating composition in an amount of 3 to 30% by weight, preferably 4 to 10% by weight, the anticorrosive property is greatly improved and the water resistance is improved in the immersion environment. If the amount of the aluminum powder exceeds the above range, the viscosity of the coating composition increases with the improvement of the anticorrosiveness, but as a result, the kneading properties during paint production and the ease of handling during the painting process tend to be lowered.

Non-tartar type epoxy resin coating composition (bittar type epoxy resin coating) is a composition containing (1) composition (I) containing epoxy resin component (a) and vinyl chloride copolymer (b), and hardening | curing agent component (c). Composition (II-a), which is used in the form of a 2-liquid (2-part) composed of (II) or (2) a composition (Ia) comprising an epoxy resin component (a) and a vinyl chloride copolymer (b). ) And a hardener component (c). Among these, the 2-liquid (1) form is preferable.

These liquid forms are stored in separate containers and, when used, immediately mixed prior to the primer application process or mixed with a mixing nebulizer such as a two-pair mixing sprayer during the painting process.

The nontartar type epoxy resin coating composition of the present invention has excellent adhesive strength to various upper paints. As the upper paint of each part of the ship, it is particularly preferable to use the inorganic tin-based hydrolytic antifouling paint described later.

This consists of a non-tartar epoxy resin as a primer on the entire outer shell of the vessel, including (i) the bottom of the ship or (ii) the bottom and the waterline of the ship, preferably the bottom, the waterline and the outer surface, in contact with sea water. It is possible to obtain an excellent adhesive strength between the primer coating and the antifouling coating film by applying the food coating composition to form a primer coating film, and further applying the surface of the primer coating with an inorganic tin hydrolyzable antifouling coating film to form the antifouling coating film. It is desirable.

Coating method of ship shell

The coating method of the outer shell of the ship according to the present invention is (i) the bottom of the ship or (ii) the bottom and the repair of the ship is applied as a primer of the non-tartar type epoxy resin medium coating composition described later to form a primer coating film Then, it is preferable to dry a primer coating film. The treated primer coating is then further applied with the inorganic tin-based hydrolytic antifouling paint described later.

In the present invention, it is also possible to apply the entire outer shell of the ship including the bottom, the repair and the outer portion to the non-tar epoxy resin medium coating composition as a primer, and to dry the resulting primer coating. Then, the surface of the primer coating formed on (i) the bottom of the primer-treated ship or (ii) the bottom and the repair is coated with an inorganic tin-based hydrolytic antifouling paint.

The bottom of the ship is located at the deepest part of the ship and is hardly touched by the sun's rays. Therefore, this part is not suitable for the growth of moss and is not polluted with organic matter than any other part, which means that the bottom is under relatively light environmental conditions. Therefore, the flat bottom is a conventional inexpensive and economically advantageous antifouling paint (e.g., chlorinated rubber, vinyl and acrylic antifouling paint) or water, which is not an inorganic tin hydrolyzable antifouling paint having excellent antifouling properties. Can be applied with chemically degradable antifouling paints. Depending on the ship's operating environment, the flat bottoms do not need to be applied as antifouling roads.

In the present invention, it is preferable that the primer-treated outer surface (surface plate on the repair portion) is coated with the outer surface upper coating because it is required that this region is exposed to strong sunlight or rough waves and has weather resistance.

The outer top coating is preferably urethane paint, epoxy paint, acrylic paint or chlorinated polyolefin paint (chlorinated rubber paint), and urethane paint is particularly preferred.

Since the primed repairs are subjected to repeated dry-immersion, which is submerged in seawater and exposed to the atmosphere and under severe environmental conditions, it is desirable that these regions have weather resistance, water resistance and sometimes, antifouling properties. For this reason, the repair part is applied with the inorganic tin-based hydrolytic antifouling paint or the repair top paint described later.

The upper coating of the repair part is preferably a urethane paint, an epoxy paint, an acrylic paint, a chlorinated polyolefin paint (chlorinated rubber paint) or an inorganic tin-based hydrolytic antifouling paint, and an epoxy paint or an inorganic tin-based hydrolytic antifouling paint is particularly preferable. .

When painting ship shells, the following methods are available.

(1) It is preferable to apply | coat the whole outer plate which consists of a bottom part, a repair part, and an outer side part simultaneously, and to dry the resulting primer coating film. Then, (i) the bottom part or (ii) the bottom part and the repair part are coated with an inorganic tin hydrolyzable antifouling paint.

(2) Each area of the shell, that is, the bottom, the repair or the outer part, or each part of each area is coated with a primer and the inorganic tin-based hydrolytic antifouling paint ((i) the bottom, or (ii) the bottom Part and repair part), or a primer and the outer part is applied by the upper part paint or the repair part is applied by the upper part paint. After the primer is applied to the outer plate, the respective areas can be applied in duplicate as described above immediately after drying.

Next, a non-tar-type epoxy resin paint, an inorganic tin hydrolyzable antifouling paint, an outer-side top paint and a repair top paint used in the above-described coating method will be described.

Non-tar epoxy resin anticorrosive coating composition

In the non-tar epoxy resin medium coating composition used in the coating method of the ship shell according to the present invention, the pigment component and the thermoplastic resin may optionally be added to the bisphenol epoxy resin and the curing agent for the epoxy resin. In addition, various additives added to conventional coating compositions such as plasticizers, extender pigments, colored pigments, decorative pigments, solvents, curing accelerators, anti-sedimentation agents and anti-sedimentation agents may be included.

In a preferred embodiment of the present invention, it is preferable to use a non-tar epoxy resin anticorrosive coating composition using a liquid to solid bisphenol epoxy resin having an epoxy equivalent of 160 to 500.

The bisphenol epoxy resin is preferably an aromatic epoxy resin of bisphenol A type or bisphenol F type. The bisphenol epoxy resin is as described above.

The curing agent is not particularly limited as long as it reacts with the resin to be cured, and various curing agents such as amine type, carboxylic acid type, acid anhydride type and silanol type may be optionally used. At room temperature, paint the outer shell frequently. Therefore, it is preferable to use the hardening | curing agent which can harden at normal temperature, and it is especially preferable to use the amine type hardening | curing agent. The amine type hardener is as described above.

Amine type curing agents are particularly preferred polyamides, epoxy adducts of polyamide amines and modified phenol amines.

It is preferable that a bit tar type epoxy resin heavy-duty coating composition contains aluminum powder as a pigment component. Aluminum powder is as above-mentioned.

It is preferable that a bit tar type epoxy resin anticorrosive coating composition further contains a thermoplastic resin. The content of the thermoplastic resin contained in the composition is preferably in the range of 5 to 90 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent.

The thermoplastic resin acts as a mitigating agent to relieve internal tension when the non-tar epoxy resin medium coating composition (epoxy paint) is cured, thereby improving the adhesive strength between the substrate or lower coating film and the epoxy film formed from the epoxy paint. Can be.

Since the thermoplastic resin is solvent soluble and soluble in the solvent contained in the upper paint, the resin improves the adhesive strength of the epoxy film to the upper paint or relaxes the limitation of the paint gap of the epoxy paint (ie, can extend the paint gap). And the resin increases the kind of upper paint that can be applied to the epoxy film.

The thermoplastic resin relates to the vinyl chloride copolymer (b) as described above. Among the various thermoplastic resins, vinyl chloride / alkyl vinyl ether copolymers such as vinyl chloride / isobutyl vinyl ether copolymer are most preferred.

In the non-tar epoxy resin anticorrosive coating composition, various additives commonly used in conventional paints such as plasticizers, extender pigments, coloring pigments, preservative pigments, solvents, curing accelerators, antisettling agents and antisettling agents may be included in addition to the above components. Can be.

Non-tartar epoxy anticorrosive coating compositions are generally used in the form of a two-liquid (2-part) consisting of a composition (I) comprising an epoxy resin component and a composition (II) comprising a curing agent. These liquids are stored in separate containers and, when used, are immediately mixed before the primer coating process or mixed with a mixing sprayer such as a two pair sprayer during the painting process.

When using a curing agent (e.g., an amine protective curing agent of the ketamine type) that has been modified to not react with the epoxy component during the storage period, the non-tartar type epoxy resin anticorrosive coating composition may be a one-liquid type paint.

In order to manufacture a bittar type epoxy resin intermediate anticorrosive coating composition, it is preferable to mix an epoxy resin composition and a hardening | curing agent component in the equivalence ratio of 1: 0.4-1: 0.8.

Unlike tar-type epoxy resin paints, non-tar-type epoxy resin anticorrosive coating compositions hardly cause skin rashes or inflammation in workers during the coating process.

Inorganic tin-based anti-fouling paint

The non-organic hydrolyzable antifouling paint includes, for example, an antifouling paint comprising a trialkylsilyl ester copolymer (i), or a vinyl resin (ii) in which an organic acid is connected to at least one or more side chain ends by metal ester bonds. It is antifouling paint.

The trialkylsilyl ester copolymer (i) and vinyl resin (ii) which are preferably used in the present invention will be described in detail later.

(i) trialkylsilyl ester copolymers

The trialkylsilyl ester copolymer comprises 20 to 65% by weight of component units derived from trialkylsilyl esters of polymerizable unsaturated carboxylic acids and has a number average molecular weight (Mn) of 1,000 to 50,000.

Trialkylsilyl ester is represented by the following general formula (1).

In formula (I), R ₁ is an alkyl group such as hydrogen or methyl; R ₂ , R ₃ and R ₄ each represent an alkyl group having about 1 to 18 carbon atoms such as methyl, ethyl, propyl or butyl; And R ₂ , R ₃ and R ₄ may be the same or different.

Trialkylsilyl esters specifically;

R ₂ , R ₃ and R ₄ are the same as in the above formula, such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate and tributylsilyl (meth) acrylate. Trialkylsilyl esters; And

In which R ₂ , R ₃ and R ₄ are different from each other trialkylsilyl esters such as dimethylpropylsilyl (meth) acrylate, monomethyldipropylsilyl (meth) acrylate and methylethylpropylsilyl (meth) acrylate do.

These trialkylsilyl esters may be used alone or in combination of two or more. The trialkylsilyl ester preferably has at least one alkyl group of R ₂ , R ₃ , and R ₄ having 3 or more carbon atoms, and more preferably all alkyl groups of R ₂ , R _3, and R ₄ have 4 or more carbon atoms. Do. It is also preferable that the total carbon number of R ₂ , R ₃ and R ₄ be about 5 to 21. Such trialkylsilyl esters are most preferably used with tributylsilyl (meth) acrylate in view of the ease of preparation of the ester, the film formability, the storage stability, and the wear cleaning properties of the antifouling composition using the ester.

As the monomer (comonomer) copolymerized with trialkylsilyl ester, any of the polymerizable unsaturated compounds (ethylenically unsaturated monomer) can be used. The polymerizable unsaturated compounds are specifically (such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and methoxyethyl (meth) acrylate) Meta) acrylic acid alkyl esters; Styrenes such as styrene and α-methylstyrene; Vinyl esters such as vinyl acetate and vinyl propionate. Among them, it is preferable to use methyl methacrylate (MMA). In this comonomer (ethylenically unsaturated monomer), the MMA is preferably contained at least 30% by weight, preferably at least 50% by weight.

In this copolymer, component units derived from polymerizable unsaturated compounds such as (meth) acrylic acid alkyl esters and component units derived from trialkylsilyl esters are randomized by cleaving the ethylene bonds of each monomer used as starting material. Combined.

In this membrane-forming copolymer, component units derived from one or more trialkylsilyl esters of polymerizable unsaturated carboxylic acids (trialkylsilyl ester component units) can be included as described above, and trialkylsilyl ester component units 20 to 65% by weight, preferably 30 to 55% by weight is included. When the component unit is included in the above content, an antifouling film having excellent antifouling property for a long time can be formed from an antifouling coating composition comprising the copolymer.

The copolymer has a number average molecular weight (Mn) of 1,000 to 50,000, preferably 2,000 to 20,000, more preferably 2,500 to 15,000, particularly more preferably 3,000 to 12,000 as measured by GPC, and usually 1,000 to 150,000, preferably Preferably the copolymer has a weight average molecular weight (Mw) of 2,000 to 60,000, more preferably 3,000 to 30,000. The copolymer has a molecular weight distribution (Mw / Mn) of usually 1.0 to 4.0, preferably 1.0 to 3.0, more preferably 1.0 It is preferable that it is -2.5. In addition, the copolymer has a glass transition temperature (Tg) of usually 15 to 80 ° C, preferably 25 to 80 ° C, more preferably 30 to 70 ° C, particularly preferably 35 to 60 ° C, for example 50%. The viscosity in the xylene solution (25 ° C.) is usually 30 to 1,000 cPs, preferably 40 to 600 cPs.

Membrane-forming copolymers, such as tributylsilyl methacrylate, in an inert atmosphere (eg, nitrogen atmosphere) at about 50-120 ° C. for about 2-12 hours, depending on the radical polymerization process. The trialkylsilyl ester may be prepared in the presence of an azo type (eg 2,2'-azobisisobutyronitrile) or a peroxy type polymerization initiator (and if necessary a presence of a polymerization modifier such as n-octyl mercaptan). Under) reacting with a polymerizable unsaturated compound (comonomer) comprising at least 50% by weight (eg 80% by weight) of methyl methacrylate in an organic solvent such as xylene.

In the film-forming copolymer obtained above, the component unit is included in an amount corresponding to the amount of each monomer.

(ii) vinyl resin

Preferred vinyl resins (ii) to be included in the inorganic tin-based hydrolytic antifouling paint used in the present invention are vinyl resins in which an organic acid comprises an organic acid connected to at least one or more side chain ends by metal ester bonds.

The vinyl resin (ii) specifically includes the vinyl resins described in Japanese Patent Laid-Open No. 73536/1996 and Japanese Patent Publication No. 108927/1995.

As described in Japanese Patent Application Laid-Open No. 73536/1996, vinyl resin (ii) is a branched alkyl group having 4 or more carbon atoms or 6 or more carbon atoms in which the alcohol residue of the ester has at least one or more side chains at the second to fourth carbon atoms from the main chain terminal. A (meth) acrylic acid ester comprising a cycloalkyl group is copolymerized with a polymerizable unsaturated organic acid monomer and a neutral polymerizable unsaturated monomer to synthesize a base resin; And acid groups of basic resins (e.g., -COOH, -SO ₃ H) are added to metal compounds (e.g. metal oxides, metal hydroxides, metal chlorides, metal sulfides) and monobasic organic acids (e.g. acetic acid, naph And the basic resin can be produced by reacting with a metal salt of monobasic organic acid.

(Meth) acrylic acid esters specifically include t-butyl (meth) acrylate and cyclohexyl (meth) acrylate. The polymerizable organic acid monomers specifically include (meth) acrylic acid, maleic acid and p-styrenesulfoninic acid. Neutral polymerizable unsaturated monomers specifically include ethylene, methyl (meth) acrylate and ethyl (meth) acrylate. The metal for forming the metal compound specifically includes a divalent or higher polyvalent metal such as Cu, Zn, Mn, Ca, Fe, Al, Te, and Ba.

Top surface paint

Specifically, the upper surface paint may be oil (alkyd) paint, phthalic acid paint, chlorinated polyolefin paint (chlorinated rubber paint), vinyl paint, acrylic paint, epoxy paint, urethane paint, silicone alkyd paint, acrylic silicone paint, and fluorine resin paint. Include.

Among them, urethane paints, epoxy paints, acrylic paints or chlorinated polyolefin paints (chlorinated rubber paints) are preferably used as the outermost top paints in consideration of weather resistance, adhesive strength and economic advantages.

The outer surface top coating is particularly specifically traded under the trade names Uny Marin (isocyanate crosslinked two-component urethane resin topcoat), Epicon Marine top coat and Epicon Marine HB (modified polyamide crosslinked two-component epoxy). Resin top coat), Ravax top coat (chlorinated polyolefin top coat), and Acry 700 top coat (acrylic resin top coat) can be purchased from Chugoku Marine Paint Co., Ltd.

Upper part paint

As the repair top paint, inorganic tin-based anti-fouling paint may be used in addition to the various outer top paints mentioned above.

Water resistance, weather resistance, corrosion resistance, and sometimes anti-pollution are required under such severe environmental conditions as the ship repeatedly climbs up and down, as in the outer shell of the ship, and is in a repetitive dry-humid condition that is submerged in seawater and exposed to the atmosphere. Therefore, in the above paints, it is preferable that urethane paint, epoxy paint, acrylic paint, chlorinated polyolefin paint (chlorinated rubber paint) or inorganic tin-based antifouling paint are used as the upper portion of the repair portion.

The repair top coatings are in particular under the trade names Unni Marine (isocyanate crosslinked 2-component urethane resin topcoat), Epicon Marine top coat and Epiconmarine HB (modified polyamide crosslinked 2-component epoxy resin topcoat), and Cree 700 top coat (acrylic resin upper coating) can be purchased from Chugoku Marine Paint Co., Ltd.

The top paint used in the present invention may include various components added to conventional shell paint such as antifouling agents, plasticizers, hydrolysis regulators, pigments, solvents, viscosity modifiers and other additives.

In the present invention, the non-tar epoxy resin coating composition (medium coating composition) or the upper coating, for example, conventional coating method using an airless spray (airless spray), air spray method, brush method or roller method Is applied to the surface of the ship's outer shell and cured to form a coating film (cured film). Prior to primer treatment, the surface is cleaned by removing material attached to the surface of the shell such as rust, fat, oils, moisture, dust, mud and salt. Paints may be diluted with a thinner or similar to a suitable concentration.

The coating weight (quantity) of the paint varies depending on the type of ship to be applied, the type of paint to be applied repeatedly, and the combination of the paint, and cannot be discriminated differently. However, the non-tar epoxy resin anticorrosive coating composition (primer) is applied in an amount of 100 to 500 g / m ² , for example, with a coating thickness of about 50 to 500 μm so that the dry film thickness becomes about 30 to 300 μm. do.

The thickness of the dry film by applying the inorganic tin-based hydrolytic antifouling paint to the primer coating on the bottom and the waterline of the ship at an application thickness of about 50 to 500 μm in an amount of about 200 to 800 g / m ² , for example. It is set to about 30-300 micrometers.

The urethane paint is applied to the primer coating on the outer surface of the ship at an application thickness of, for example, 50 to 300 g / m ² , so that the dry coating thickness is about 30 to 150 μm.

In the air spray coating method, the coating conditions of the primary pressure (air) of about 4 to 8 kgf / cm 2, the secondary pressure (paint) of about 100 to 180 kgf / cm 2 and the injector movement speed of about 50 to 120 cm / sec Set.

The number of coatings of each coating is not particularly limited and may be arbitrarily determined according to the concentration of the coating, the thickness of the desired coating, and the like. Each paint can be applied one or more times.

Vessels having the above-described thickness formed by coating and curing with the paint include, for example, metal vessels such as tankers, cargo ships, ships, fishing vessels, barges and floating docks.

If the non-tar epoxy resin coating composition with excellent overcoatability is used as a primer not only for the shell but also for other parts such as exposed deck, upper structure (housing), hold and ballast tanks. If so, the type of paint used for the whole ship can be greatly reduced.

If the deck, the upper structural part (housing), the hold part and the ballast tank part as well as the ship shell are applied with the same primer for applying the bottom, and then applied with the same primer for overlapping, the effect of the present invention can be further increased.

By virtue of the non-tar epoxy resin coating composition according to the present invention, the outer shell or other parts of the ship have various functions, such as corrosion resistance, weather resistance, It can have water resistance and pollution prevention. Unlike the tar type epoxy resin medium coating composition, the coating composition of the present invention does not cause bleeding, and thus does not cause deterioration of aesthetics or deterioration of contamination resistance in the upper coating film. Therefore, there is no need to protect the boundary between different areas.

In addition, the coating film (medium coating film) formed from the non-tar epoxy resin coating composition (medium coating coating composition) can be used for various top coatings (for example, inorganic tin-based hydrolytic antifouling coatings, chlorinated rubber, urethane and epoxy coatings). Since it has excellent adhesive strength with respect to the coating film of), and there is no bleeding unlike a tar type coating material, there is no fall of aesthetics and a fall of antifouling property. Therefore, the medium coating composition can be used for both the submerged and exposed areas of the ship shell, which replaces the conventional primers for various ship parts, such as the shell and exposed deck, with one type of the double coating composition. It can streamline the painting process and protect the labor force.

If a top coating such as an inorganic tin-based hydrolytic antifouling coating is further applied to the coating film of the non-tar type epoxy resin coating composition, various top coatings may be used at long time intervals. Moreover, the coating film of the coating composition of the present invention has excellent adhesion strength to the coatings of various upper paints. Therefore, the step of applying the binder paint (intermediate paint) before applying the upper paint can be omitted, thereby streamlining the ship-painting or ship-building process and reducing the cost of storing and storing the paint.

Unlike conventional tar-type epoxy resin coatings, the non-tar-type epoxy resin coating compositions are beneficial to the hygiene and environmental protection of painters with little incidence of skin rash or irritation of the worker during the coating process.

In the coating method of the ship shell according to the present invention, the coating film excellent in antifouling property can be formed using a small kind of paint including a non-tar epoxy resin medium anticorrosive coating composition and an inorganic tin hydrolyzable antifouling coating. . Therefore, the method can reduce the painting time and reduce the cost of storing the paint, which is advantageous for the sanitary and environmental protection of the painter. Ships painted in that way, in particular the shell of a ship, have good antifouling properties.

Example

The present invention will be described in more detail according to the following examples, but the present invention is not limited to these examples.

In the following examples, film thickness (μm) means dry film thickness without departing from the nature of the present invention. The term part means part by weight.

In the following table, the contents of each component are expressed in parts by weight unless otherwise noted.

Preparation of Non-tartar Type Epoxy Coating

A main agent (composition comprising an epoxy resin) and a curing agent (composition comprising a hardening agent component) of each of the non-tartar type epoxy resin intermediate coating compositions of the mixing ratios disclosed in Table 1 were prepared.

When preparing each of the non-tar-type epoxy resin medium coating compositions of the mixing ratios disclosed in Table 1, the main ingredient was prepared by sufficiently mixing the components using a paint mixer using glass beads, and the curing agent was prepared by using a high speed sprayer. Was prepared by mixing uniformly.

Coating of the non-tar epoxy resin anticorrosive coating composition is performed immediately after mixing the main material and the curing agent in the mixing ratios (per weight) described in Table 1.

Medium anticorrosive coating composition Example OT-1 OT-2 (A) OT-2 (B) OT-3 PT-4 OT-5 OT-6 OT-7 Topic Epicorte 828 Epicorte 834-85x Epicorte 1001-70 Laroflex MP-25 TCP Talc NKK Tar Liquid Oxidized Red Iron Alpha 1900xs Disparon 6600 Xylene MIBK Methoxypropanol 1-Butanol 203330271.514.522 1583327271.514.522 1583327271.514.522 2053252101.514.522 23.56330571.59.5222 23.53330571.512.5222 2963205101.511222 2963205101.511222 Hardener Luckamide TD966TAP Adeca hardener EH 350 150.3 150.3 150.3 150.3 120.3 200.6 250.6 -0.28 Mixed non-topic in the painting process: Hardener (per weight) 85: 15.3 85: 15.3 73: 8.3 85: 15.3 91.5: 12.3 91.5: 20.6 91.5: 25.6 91.5: 8.2

Medium anticorrosive coating composition Comparative example Reference Example H-1 H-2 E-2 Topic Epicorte 828 Epicorte 834-85x Epicorte 1001-70 Laroflex MP-25 TCP Talc NKK Tar Liquid Oxidized Red Iron Alpha 1900xs Disparon 6600 Xylene MIBK Methoxypropanol 1-Butanol 19282251.513.54 23.5335571.514222 5173571.5178 Hardener Luckamide TD966TAP Adeca hardener EH 350 70.3 120.3 100.2 Mixed non-topic in the painting process: Hardener (per weight) 93: 7.3 95: 12.3 90.5: 10.2

Starting materials disclosed in Table 1 are as follows.

(1) Epicorte 828 (trade name)

Available from Cell Chemical Co., Ltd., bisphenol A type,

Liquid epoxy resin (epoxy equivalent: 180-190)

(2) Epicorte 834-85x (trade name)

Available from Cell Chemical Co., Ltd., bisphenol A type,

Semi-solid epoxy resin (epoxy equivalent: 290 to 310,

Solvent: Xylene, Nonvolatile Components (NV): 85%)

(3) Epicorte 1001-70 (trade name)

Available from Cell Chemical Co., Ltd., bisphenol A type,

Solid epoxy resin (epoxy equivalent: 660-690,

Solvent: Xylene / Toluene / MIBK, NV: 70%)

(4) Laroflex MP-25 (trade name)

I can purchase it from BASF Corporation,

Vinyl Chloride / Vinyl Isobutyl Ether Copolymer (Mw: 28,000-30,000)

(5) TCP

Available from Mitsubishi Gas Kagyo High School, Tricresyl Phosphate

(6) Talc NKK (trade name)

We can purchase from Fuji Talc High School

(7) tar

Available from BO Chemical Co., Ltd., bojuntan varnish

(Solvent: Xylene, NV: 70%)

(8) Disparon 6600 (trade name)

Available from Kusumoto Kasei High School, thixotropic agent of powdered polyamide

(9) red iron oxide

Trade name: bengara tsubame,

We can purchase from Bengara Japan High School.

(10) Alfa Ste 1900xs (trade name)

Available from Toyo Aluminum High School, leaf-shaped aluminum (NV: 75%, solvent: xylene / terpene)

(11) Luckamide TD-966 (trade name)

It is available for purchase from Japan ink and chemical company,

Polyamide (amine number: 150-190, NV: 60%, solvent: xylene / 1-butanol)

(12) Adeka hardener EH350 (trade name)

It is available for purchase from Asai Tenka Koga Senior High School,

Modified polyamine (amine number: 330-380, NV: 100%)

(13) TAP (trade name)

It is available for purchase from Kayaku Akuejo High School,

t-amine (amine number: 620)

(14) MIBK (methyl isobutyl ketone)

Discoloration resistance test of upper paint

For testing, a surface of a sanded steel sheet (70 × 150 × 2.3 mm) with an injector was applied with a non-tar epoxy resin medium coating composition (primer) by air spraying so that the dry film thickness was 200 μm. Dry at 24 ° C. for 24 hours. Then, the surface of the resulting coating film was coated with an chlorinated polyolefin-type white upper coating (trade name: Lavax Top Coat White, available from Chugoku Marine Paint Co., Ltd.) by air spraying to obtain a dry coating thickness of 50 µm and then 20 ° C. Dry for 24 hours to obtain a test plate. The test plate was placed in an outdoor exposure stand (according to JIS K5400 9.9) installed at the Otage Research Center (Otake City, Hiroshima Prefecture) of Chugoku Marine Paint Co., Ltd. to expose the surface of the coating film to the outside, and the external exposure experiment was conducted for 30 days. . Then, the degree of discoloration of the upper coating film was evaluated by visual observation.

The results are shown in Table 2.

Medium anticorrosive coating composition (primer) Discoloration state of the upper coating film OT-1 Not observed OT-2 (A) Not observed OT-2 (B) Not observed OT-3 Not observed OT-4 Not observed OT-5 Not observed OT-6 Not observed OT-7 Not observed H-1 Discoloration very much H-2 Not observed E-2 Not observed

As can be seen clearly from the above results, the medium anticorrosive coating compositions OT-1 to OT-7 are excellent in the discoloration resistance of the upper coating film, and the aesthetics of the upper coating film of the outer surface portion and the repair portion are not lowered.

Anticorrosive test

A steel plate (70 x 150 x 2.3 mm) sanded with an injector was applied using an air spray method with a test paint so that the dry film thickness was 200 µm, and dried at 20 DEG C for 7 days to obtain a test plate.

The test plate was soaked in 3% brine at 40 ° C. for 180 days. Thereafter, the degree of blistering and rusting was evaluated by visual observation in accordance with ASTM D714-56 and ASTM D610-85, respectively, and the adhesive strength was measured by cross-cutting adhesive strength test in accordance with JIS K5400 8. 5. 2. -cut adhesive test).

The results are shown in Table 3.

Evaluation table of foaming test

10: no foaming observed

9: The foam area with a diameter of 0.5 mm is less than about 0.2% of the total area of the test plate.

8: A foam area having a diameter of 0.5 mm is about 0.5% of the total area of the test plate.

7: The foamed area having a diameter of 0.5 to 1 mm is about 0.5% of the total area of the test plate.

6: The foaming zone having a diameter of 1 to 2 mm is about 0.5 to 1% of the total area of the test plate.

5: The foaming zone having a diameter of 2-3 mm is about 1-5% of the total area of the test plate.

4: A foamed area having a diameter of 3 to 5 mm is about 5 to 10% of the total area of the test plate.

3: The foamed area having a diameter of 3 to 5 mm is about 10 to 15% of the total area of the test plate.

2: A foamed area having a diameter of 3-5 mm is 15-30% of the total area of the test plate.

1: The rust-foaming area is more than 30% of the total area of the test plate.

Evaluation table of rust generation test (ASTM D610-85)

10: No rust was observed or the rusted area is less than 0.03% of the total area of the test plate.

9: Rusted area is more than 0.03% and less than 0.1% of the total area of the test plate.

8: Rusty area is more than 0.1% and less than 0.3% of the total area of the test plate.

7: Rusty area is more than 0.3% and less than 1% of the total area of the trial.

6: Rusty area is more than 1% and less than 3% of the total area of the trial.

5: Rusty area is more than 3% and less than 10% of the total area of the trial.

4: Rusty area is more than 10% and less than 16% of the total area of the trial.

3: Rusty area is more than 16% and less than 33% of the total area of the trial.

2: Rusty area is more than 33% and less than 50% of the total area of the trial.

1: Rusty area is more than 50% of the total area of the trial.

Evaluation table of cross-cut adhesive strength test

10: each cut line is good; Both sides of each cutting line are smooth; And no peeling was observed at any intersection and any area of the cutting line.

9: Each cut line is slightly thicker.

8: Slight peeling is observed at the intersection of the cutting lines; No area peeling was observed; The damage area is less than 5% of the total area.

7: Peeling is observed at the intersection with both sides of the cutting line; And the area of the damage site is 5% or less of the total area.

6: Peeling is observed at both intersections of the cutting line; The damage area is 5 to 15% of the total area.

5: the extent of exfoliation caused by cleavage is wider than six; The damage area is 15-25% of the total area.

4: the extent of exfoliation caused by cutting is wide; The damage area is 25 to 35% of the total area.

3: area peeling is observed; The damage area is less than 35% of the total area.

2: the extent of exfoliation caused by cutting is wider than that of 3; The damage area is 35 to 50% of the total area.

1: the extent of exfoliation caused by cutting is wider than that of 2; The damage area is 50 to 70% of the total area.

0: The area of damage is 70% or more of the total area.

Medium anticorrosive coating composition Anticorrosive test firing rust Adhesive strength OT-1 10 10 10 OT-2 (A) 10 10 10 OT-2 (B) 10 10 10 OT-3 10 10 10 OT-4 10 10 10 OT-5 10 10 10 OT-6 10 10 10 OT-7 10 10 10 H-1 10 10 10 H-2 10 10 10 E-2 5 7 9

As can be seen clearly from the results shown in Table 3, the heavy anticorrosive coating compositions OT-1 to OT-7 exhibited the same or more corrosion resistance as those of the tar type epoxy resin heavy anticorrosive coating composition.

Topological test

Adhesion Strength Test for Various Top Paints

A sanded steel sheet (70 x 150 x 2.3 mm) with an injector was applied as a test paint (primer) using the air spray method so that the dry film thickness was 200 mu m. The plate was then placed on an outdoor exposure stand (according to JIS K5400 9.9) installed at the Otake Research Center of Chugoku Marine Paint Co., Ltd. Outdoor exposure was performed. Thereafter, the plate was coated with various upper paints disclosed in Table 4 using an air blowing method so that the dry film thickness was 50 μm and dried at 20 ° C. for 7 days to obtain a test plate.

The test plate was soaked in 3% brine at 20 ° C. for 90 days, and the adhesive strength to the upper coating was evaluated by a cross-cut adhesion test (according to JIS K5400 8. 5.2) in the same manner as described above.

The results are shown in Table 4.

** Discoloration (browning) of the upper paint was observed in the H-1 paint system of Table 4.

* 1: Chlorinated polyolefin upper paint (1-component),

It is available for purchase from Chugoku Marine Paint

* 2: isocyanate crosslinked two-component urethane upper paint,

It is available for purchase from Chugoku Marine Paint

* 3: modified polyamide crosslinked two-component epoxy upper coating,

It is available for purchase from Chugoku Marine Paint

As can be clearly seen from the results in Table 4, the medium anticorrosive coating compositions OT-1 to OT-7 exhibit excellent topological properties for various top coatings.

Preparation of Inorganic Tin Hydrolyzable Antifouling Paint

An antifouling coating composition having a formulation ratio disclosed in Table 5 was prepared. In Table 5, the content of each component is expressed in parts by weight.

Preparation of each antifouling paint composition having the formulation ratios disclosed in Table 5, the components were mixed for 2 hours with a paint mixer comprising glass beads, and aged for 12 hours at room temperature. Then, the resultant mixture was filtered with a 100 mesh filter to obtain a desired inorganic tin-based hydrolytic antifouling coating composition.

The components disclosed in Table 5 are as follows.

(1) S-3 varnish

Trialkylsilyl ester copolymer solution, composition of monomer in polymer: tributylsilyl methacrylate / methyl methacrylate = 50/50 (weight ratio), solvent: xylene, heating residue: 49.6 weight%, viscosity: 259 cPs / 25 ℃

(2) BL-1 varnish

Styrene acrylic ester copolymer solution, monomer in polymer: isobutyl methacrylate / t-butyl methacrylate / styrene / stearyl methacrylate = 30/30/30/10 (weight ratio), heating residue: 50% by weight, Viscosity: A ₄ (Gardner / 25 ℃)

(3) Toyo Farax 150 (trade name)

Available from Tosoh High School, Chlorinated Paraffin, Average Number of Carboatoms: 14.5, Chlorine Content: 50%, Viscosity: 12 Poises / 25 ° C, Specific Gravity: 1.25 / 25 ° C

(4) Mika Shiratama (trade name)

Available from Wakimoto Mica, Leaf-shaped pigment, Average particle size: 15㎛,

Aspect ratio: 40

(5) molecular sieve 4A (trade name)

Dehydrating agent, available from Union Showa High School, Synthetic Zeolite Powder

(6) Disparon 305 (trade name)

Available from Kusumoto Chemical Co., Ltd., hydrogenated caster oil anti-sagging agent

(7) Disparon 4200-20 (trade name)

Available from Kusumoto Chemical Co., Ltd., polyethylene oxide sedimentation inhibitor, 20% xylene paste

Adhesive strength to antifouling paints

A steel plate (70 x 150 x 2.3 mm) sanded with an injector was applied as a test paint (primer) using an air spray method so as to have a dry film thickness of 200 mu m. Then, the plate was placed in an outdoor exposure stand (according to JIS K5400 9.9) installed in the Otake Research Center of Chugoku Marine Paint Co., Ltd. An outdoor exposure test was performed for days. Thereafter, the plate was coated with an inorganic tin paint (AF-1 or AF-2) using an air blowing method so that the dry film thickness was 100 μm, and dried at 20 ° C. for 7 days to obtain a test plate.

After immersing the test plate in natural seawater for 180 days, the adhesive strength to the inorganic tin-based hydrolytic antifouling paint was evaluated by a cross-cut adhesive strength test (according to JIS K5400 8. 5.2).

The results are shown in Table 6.

Medium anticorrosive coating composition Adhesion of Non-organic Tin Hydrolyzable Antifouling Paint AF-1 AF-2 OT-1 10 10 OT-2 (A) 10 10 OT-2 (B) 10 10 OT-3 10 10 OT-4 10 10 OT-5 10 10 OT-6 10 10 OT-7 10 10 H-1 0 0 H-2 2 2 E-2 2 2

Pollution Prevention and Consumption of Anti-fouling Paint System

A sanded plate (70 × 20 × 3 mm) was bent and placed on the side of a rotating drum installed in the waters of Hiroshima Bay.

The sanded plate was applied to a dry tar thickness of 200 μm by air blowing using a non-tar epoxy resin coating composition, and dried at 20 ° C. for 2 days. Thereafter, the plate was coated with an inorganic tin hydrolyzable antifouling paint using an applicator to have a dry film thickness of 200 μm, and dried at 20 ° C. for 7 days to obtain a test plate.

In order to compare with the said coating method of this invention, the conventional coating method is performed by the following method. The sanded plate was applied with a two-component tar epoxy heavy-duty paint composition (trade name: Viscon AC, available from Chugoku Marine Paint Co., Ltd.) using an air spraying method to obtain a dry film thickness of 150 μm, followed by 2 at 20 ° C. Dried for days. The plate was then applied with a vinyl binder paint (trade name: Silvacs SQK, available from Chugoku Marine Paint Co., Ltd.) using an air spray method to achieve a dry film thickness of 50 μm and dried at 20 ° C. for 2 days. It was. Thereafter, the plate was further coated with an inorganic tin hydrolyzable antifouling paint using an applicator to have a dry film thickness of 200 μm, and dried at 20 ° C. for 7 days to obtain a test plate.

Each of the test plates manufactured above was placed on a rotating drum and the ship was simulated at a speed of 15 knots for 12 months under 50% operating conditions (12 hours at night and 12 hours during the day) to prevent contamination (operating contamination). The resistance, the ratio (%) of the adhesion area of various aquatic organisms to the test plate) and the degree of consumption (reduction of the film thickness (µm)) were evaluated.

The results are shown in Tables 7 and 8.

Medium anticorrosive coating composition (primer) Pollution Prevention: Attachment Area (%) AF-1 AF-2 OT-1 0 0 OT-2 (A) 0 0 OT-2 (B) 0 0 OT-3 0 0 OT-4 0 0 OT-5 0 0 OT-6 0 0 OT-7 0 0 H-1 20 20 H-2 0 0 E-2 0 0 Conventional paint system (tar epoxy heavy paint coating composition and binder paint) 0 0

Note: AF-1 and AF-2 are inorganic tin-based antifouling paints listed in Table 5.

Medium anticorrosive coating composition (primer) Consumption degree: ㎛ AF-1 AF-2 OT-1 55 59 OT-2 (A) 56 56 OT-2 (B) 56 56 OT-3 53 54 OT-4 55 59 OT-5 53 56 OT-6 54 55 OT-7 53 54 H-1 34 31 H-2 50 54 E-2 52 55 Conventional paint system (tar epoxy heavy paint coating composition and binder paint) 51 53

Note: AF-1 and AF-2 are inorganic tin-based antifouling paints shown in Table 5.

As can be clearly seen from the results of Tables 7 and 8, the medium anticorrosive coating compositions OT-1 to OT-7 are more than equivalent to those of the conventional coating system, even if none of the bonding paints required in the conventional coating system are used. It is possible to provide paint systems with performance and consumption levels.

The effect of reducing the number of coatings, the number of paints and the number of diluents

The coating method of the present invention was compared with the conventional method with respect to the number of coatings, the type of paint and the number of diluents.

The comparison of labor savings in the painting process between the coating method of the present invention and the conventional coating method is shown by applying the inorganic tin-based hydrolytic anti-fouling paint to the bottom part and the repair part of the newly constructed 75,000 ton transport ship as shown in Table 9. Was performed (life of coating: 2 years).

Coating method using the paint of the present invention Kind of paint Number of paintings Bottom and repair Non-tar epoxy resin anticorrosive coating composition 2 Inorganic tin-based anti-fouling paint 2 External Non-tar epoxy resin anticorrosive coating composition One Urethane Upper Paint One The total number of kinds of paint 3 Total Coating Count 6 Total number of diluent types 3

Coating method-1 using conventional paint Kind of paint Number of paintings Bottom and repair Tar Type Epoxy Resin Heavy Anticorrosive Coating Composition One Vinyl resin binder paint 2 Inorganic tin-based anti-fouling paint 2 External Chlorinated Rubber Anticorrosive Coating Composition 2 Chlorinated Rubber Paint 2 The total number of kinds of paint 5 Total Coating Count 9 Total number of diluent types 4 (When using a diluent for an inorganic tin-based hydrolytic antifouling paint and a chlorinated rubber paint composition and a diluent for a chlorinated rubber upper paint: 3)

Coating method using conventional paint-2 Kind of paint Number of paintings Bottom and repair Tar Type Epoxy Resin Heavy Anticorrosive Coating Composition 2 Vinyl resin binder paint One Inorganic tin-based anti-fouling paint 2 External Epoxy Resin Heavy Anticorrosive Coating Composition 2 Epoxy Resin Top Paint 2 Number of paint types 5 Number of paintings 9 Number of diluent types 3 (The diluent for tar type epoxy resin intermediate coating composition and the epoxy resin coating composition and diluent for epoxy resin upper coating can be commonly used.)

Rationalization of the Painting Process by the Method of the Present Invention

In the outer coating process of the newly constructed 75,000 ton transport ship, the above-described coating method according to the present invention was compared with the conventional coating method-1 to evaluate the degree of rationalization with the following items.

Regarding the degree of rationalization, the coating method of the present invention was evaluated based on 100 of the conventional coating method-1.

1. Painting work time

The period required to apply the paint by the airless spray method was evaluated. This period does not include time to prepare the painting tools, but includes the time the worker moves on the scaffold or transporter for high-rise work.

2. Inefficient operation

The following inefficient work was evaluated.

(1) Cleaning of painting machines or painting tools related to paint replacement and paint replacement.

(2) The need for protection or management of redundant spraying for the use of other paints in the paint-replacement area.

(3) Movement of workers, preparation of the painting process, and cleaning or repositioning after painting.

3. Failure of the painting

Failure to paint due to incorrect choice of paint, failure to spray to the paint-replacement area and wrong choice of thinner were evaluated.

4. Process control work

The labor required to control the paint spacing, the other processes (block construction or transfer) and the labor to control the proper placement of the painting process, and the labor to control the placement of the workers were evaluated.

5. Paint storage and management work

Work on ordering, receiving, sorting, and rearranging paints and thinners was evaluated.

6. Loss of paint and thinner, disposal of waste paint and waste diluent

The loss of paints and diluents due to the replacement of paints, the loss of paints due to overuse when using multiple paints, the increase of unusable paints due to the remaining paint in the container, and the treatment of waste paints and diluents were evaluated. .

The results are shown in Table 10.

Rationalization degree Coating method using the paint of the present invention Coating method-1 using conventional paint 1. Coating time 70 100 2. Inefficient operation 70 100 3. Painting failure 90 100 4. Process Control 80 100 5. Storage and management of paint 80 100 6. Loss of paint and thinner, disposal of waste paint and waste diluent 50 100

As is apparent from the above results, the rationalization of the coating process of the ship shell is feasible by using the coating method using the paint of the present invention.

As is apparent from the above results, the rationalization of the coating process of the ship shell is feasible by using the coating method of the present invention.

In addition, rationalization can be increased by using the non-tartar type epoxy resin anticorrosive coating composition of the present invention as a primer for other vessel parts besides the shell plate.

Moreover, since the area of the same paint can be expanded to stabilize the painting technique required for the painter, a uniform high quality coating can be easily obtained, and further, a great advantage can be obtained such as an improvement in working efficiency.

Claims (28)

(a) bisphenol epoxy resins, (b) vinyl chloride copolymer, and (c) a curing agent comprising polyamide or modified product thereof Bittar type epoxy resin coating composition comprising a. The coating composition according to claim 1, wherein the bisphenol epoxy resin (a) has an epoxy equivalent of 100 to 500. The coating composition according to claim 1 or 2, wherein the coating composition further comprises aluminum powder (d) in addition to components (a), (b) and (c). The coating composition according to any one of claims 1 to 3, wherein the vinyl chloride copolymer is a vinyl chloride / alkyl vinyl ether copolymer. The coating composition according to any one of claims 1 to 4, wherein the coating composition comprises tricresyl phosphate. The coating composition according to any one of claims 1 to 5, comprising as a curing agent a mixture of polyamide or its modified substance with other curing agent components. The coating composition according to any one of claims 1 to 6, wherein the coating composition is used as a medium anticorrosive coating composition. The medium anticorrosive coating film formed from the coating composition of any one of Claims 1-7. (i) the bottom of the ship or (ii) the bottom and the repair of the ship are applied with a non-tar epoxy resin anticorrosive coating composition as a primer to form a primer coating film; And And coating the surface of the primer coating film with an inorganic tin-based hydrolytic antifouling paint. Applying the entire outer shell of the ship including the bottom, the repair and the outer portion to the non-tar epoxy resin anticorrosive coating composition as a primer to form a primer coating film; And The coating method of the ship shell which contains the step of apply | coating the surface of the primer coating film formed in (i) bottom part or (ii) bottom part and repair part of the said primer-treated outer plate with an inorganic tin-based hydrolytic antifouling paint. Applying the entire tarpaulin of the ship including the bottom, the repair part and the outer part to the non-tar epoxy resin anticorrosive coating composition to form a primer coating film; The surface of the primer coating film formed on the (i) bottom part or (ii) bottom part and the repair part of the primer-treated outer plate is further coated with an inorganic tin-based hydrolytic antifouling paint, and the surface of the primer coating film formed on the outer part part is applied. Applied with an outer top paint; And optionally The coating method of the outer shell of the ship comprising the step of further coating the repair portion with the upper portion paint. The coating method of the ship shell of any one of Claims 9-11 in which the non-tar epoxy resin medium anticorrosive coating composition further contains a thermoplastic resin. 13. The method of coating a ship shell according to claim 12, wherein the thermoplastic resin is at least one resin selected from chlorinated polyolefins, acrylic resins, biryl acetate resins, styrene resins and vinyl chloride resins. The method of coating a ship shell according to claim 13, wherein the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer. The coating method of the ship shell of any one of Claims 9-14 in which a bittar-type epoxy resin medium anticorrosive coating composition contains aluminum powder. 12. The top surface paint of claim 11 is a urethane paint, an epoxy paint, an acrylic paint or a chlorinated polyolefin paint, and the repair top paint is a urethane paint, an epoxy paint, an acrylic paint, a chlorinated polyolefin paint or an inorganic tin antifouling paint. Coating method of ship shell. The inorganic tin-based antifouling paint according to any one of claims 9 to 16, comprising 20 to 65% by weight of component units derived from trialkylsilyl esters of polymerizable unsaturated carboxylic acids, A coating method of a ship shell containing a trialkylsilyl ester copolymer having a number average molecular weight (Mn). The coating method according to any one of claims 9 to 17, wherein the inorganic tin-based hydrolytic antifouling paint comprises a vinyl resin in which an organic acid is connected to at least one or more side chain ends by metal ester bonds. A non-tar epoxy resin medium primer coating film formed on the bottom of the ship (i) or the bottom and the waterline of the ship (ii), and A painted vessel having an inorganic tin-based hydrolytic antifouling coating formed on the primer coating. Bittar-type epoxy resin medium anticorrosive primer coating film formed on the entire outer shell of ship including bottom, repair and outer part, and A painted vessel having an inorganic tin-based hydrolyzable antifouling coating formed on the outer (i) bottom of the entire primer coating or (ii) the primer coating of the bottom and repair. Bittar type epoxy resin medium anticorrosive primer coating film formed on the entire outer shell of the ship including bottom, repair and outer part, (i) a bottom portion or (ii) an inorganic tin hydrolyzable antifouling coating formed on the primer coating of the bottom and the repair portion, and an outer surface upper coating film formed on the primer coating of the outer surface thereof, And optionally A painted ship comprising a repair top coating formed further on the repair. 22. The painted vessel according to any one of claims 19 to 21, wherein the bittar-type epoxy resin medium anticorrosive primer coating further comprises a thermoplastic resin. 23. The painted vessel of claim 22 wherein the thermoplastic resin is at least one resin selected from chlorinated polyolefins, acrylic resins, vinyl acetate resins, styrene resins and vinyl chloride resins. 24. The painted vessel of claim 23 wherein the vinyl chloride resin is a vinyl chloride / vinyl isobutyl ether copolymer. 25. The painted vessel according to any one of claims 19 to 24, wherein the bittar-type epoxy resin anticorrosive coating comprises aluminum powder. 22. The anti-corrosive coating according to claim 21, wherein the upper outer coating is formed of urethane, epoxy, acrylic or chlorinated polyolefin, and the upper coating is made of urethane, epoxy, acrylic or chlorinated polyolefin. Painted vessels formed with paint. 27. The number according to any one of claims 19 to 26, wherein the inorganic tin-based hydrolytic antifouling coating film contains 20 to 65% by weight of component units derived from trialkylsilyl esters of polymerizable unsaturated carboxylic acids. Painted vessel comprising a trialkylsilyl ester copolymer having an average molecular weight (Mn). 28. The painted vessel according to any one of claims 19 to 27, wherein the inorganic tin-based hydrolytic antifouling coating film comprises a vinyl resin in which an organic acid is bound to at least one or more side chain ends with metal ester bonds.