JP2000037658A - Painting method for shell of ship and ship painted thereby - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the application of only one kind of anti-corrosive paint to the shell and deck of a ship when the desired dry paint-thickness is constant, to easily control the paint-thickness, and to make superb the anti-corrosiveness of a ship, specially of its shell. SOLUTION: The application of a primer to the shell of a ship is carried out in such a way that a specific bisphenol type epoxy resin or specific urethane resin anti-corrosive paint composition is so prepared as to control a contrast ratio at a desired dry paint-thickness of t0 μm (t0 is 100 to 300) and that of t0/2 μm within a specific range, and in such a way that the application amount of the paint composition is so controlled that a color difference between the surface of wet paint film and the shell surface is adjusted to the valve of 90 or more, as visually compared to the value of 100 given as the color difference between the surface of the desired dry paint-thickness of t0 μm and the shell surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coating a ship outer plate and a coated ship, and more particularly, to an anticorrosion paint for an outer plate portion of a ship (bottom portion, water line portion and outer side portion) and a deck portion. The present invention relates to a method of coating a ship outer plate, which can be used as a single product, and which can easily control the coating thickness of the anticorrosion paint, and a ship coated by this method.

[0002]

Technical Background of the Invention A ship's outer panel is roughly divided into a ship bottom part which is always immersed in water (including fresh water and seawater), a hull part which is not immersed in water, and an intermediate part between them. And a waterline portion where immersion in the air and exposure in the air are repeated.

[0003] When painting the outer shell of such a ship, the outboard part is exposed to strong sunlight and wind waves and is required to have weather resistance. The water line portion receives strong wind waves or is repeatedly immersed in water and exposed to dry air, so that it is required to have weather resistance, water resistance and, if necessary, antifouling properties.

For this reason, conventionally, in order to apply a paint having a required function to each part, a plurality of types of special primers in consideration of adhesiveness and the like have been prepared, and the adhesion and anticorrosion of the coating system have been improved. Was secured.

Conventionally, a heavy tar-epoxy anti-corrosion paint having excellent anti-corrosion properties has been applied to the bottom of the ship and, if necessary, the portion including the water line portion. In addition, tar has a pure black hue, so that there is a problem in that it is difficult to visually discriminate corrosion after painting, burnout due to the thermal influence of welding and fusing, and the state of a coating film.

[0006] Further, in a paint containing tar, the tar content is transferred (tar bleed) to an overcoat layer coated on the coating film, which impairs the aesthetic appearance of the coated ship, and has antifouling properties, weather resistance, etc. Has the disadvantage of adversely affecting the function of the device.

[0007] A non-tar primer is generally used as a primer on the outer side of the outer plate and, if necessary, on the water line, in order to avoid tar bleed. When using tar-epoxy-based heavy-duty anticorrosive paint for the bottom and waterline primers, cure the tar / non-tar primer separately (that is, apply uncoated parts by attaching sheets or tapes). Protection), and carefully devise the wrap (the area where different types of paints overlap) to apply the paint. In addition, when using a different paint,
It was necessary to wash the coating machine (apparatus) sufficiently, which required complicated steps and wasteful use of thinner.

Further, conventionally, when a non-organic tin-based hydrolyzable antifouling paint is applied on a tar epoxy-based heavy anticorrosive paint,
Due to poor mutual adhesion, non-organic tin hydrolyzable antifouling paint must be applied after applying vinyl or tar vinyl binder coat on tarepoxy heavy anticorrosive paint film Was. In addition, after applying the tar epoxy-based anticorrosion paint, when applying a topcoat on the coating film, a predetermined interval (time interval) is provided and the topcoat is applied. Since this interval is relatively short, complicated steps and construction management were required.

In addition, such a conventional method for coating a hull outer panel requires an assortment of paints of an extremely large number of brands to meet various needs of customers, and also requires troublesome construction management and the like. In addition, there are problems in that the cost of storing, transporting, and storing the paint is increased, the painting process is complicated, and the painting period is lengthened, and complicated process management is required.

As described above, in the past, it was necessary to change the anticorrosion paint for each part of the ship and for each type of topcoat paint used. However, in order to maintain the quality performance of the anticorrosion paint film, Conventionally, it has been necessary to measure and control the thickness of the anticorrosive paint after measuring it with an instrument.

[0011] For this reason, it is possible to use a single type of anticorrosion paint for the outer panel portion (ship bottom portion, water line portion and outer side plate portion) and deck portion of the ship, and the coating thickness of the anticorrosion paint. It has been desired to develop a method for coating a ship's outer panel that can easily control the ship's surface.

Japanese Patent Application Laid-Open No. Sho 62-218459 discloses that a resin and a color pigment are contained, and the opacity is determined by the dry film thickness.
0.96 or more at a μm, (a-30) μm or more a μ
m and 0.90 or less (where a is 50 to 120 μm)
m) are disclosed. According to this coating composition, while being a color pigment,
It is described that by adjusting the concealment ratio by the contained coloring pigment, the number of coatings can be reduced and the film thickness can be sufficiently controlled even by one coating.
In addition, the paint film thickness is controlled by checking the opacity and color of the base material immediately after painting, and if there is a difference in color compared to the standard color sample board, correct coating is performed on the spot and the lower limit film thickness is controlled. It is described that the film thickness can be controlled by the above coating film thickness.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and to provide an outer plate portion of a ship (a bottom portion, a water line portion, and an outer plate portion of a port), An object of the present invention is to provide a method for coating a ship outer plate, which can make a single type of anticorrosion paint on the deck portion and can easily control the thickness of the applied anticorrosion paint, and a ship coated by this method. The purpose is.

[0014]

SUMMARY OF THE INVENTION A method for coating a ship outer panel according to the present invention comprises:
(A) Undercoat and anticorrosion paint (primer) on the surface of the bottom shell (a) of the ship or the outer shell (b) of the bottom and the waterline
(I) a bisphenol type epoxy resin having an epoxy equivalent of 150 to 1000, (ii) a polyamidoamine,
A curing agent for an epoxy resin composed of a polyamine or a modified product thereof, (iii) a coloring pigment of 0.3 to 5% by weight (solid content), and (iv) a light-transmitting inorganic filler of 25 to 50% by volume (filler volume Concentration) containing an anticorrosive paint composition,
Or (v) a polyol and / or polythiol,
(Vi) a polyisocyanate-based curing agent, (iii) 0.3 to 5% by weight (solid content) of a coloring pigment, and (iv) 25 to 50% by volume (filler volume concentration) of a light-transmitting inorganic filler. The anticorrosion coating composition obtained has a hiding factor of 0.94 or more and less than 1 at a desired dry coating film thickness t ₀ μm, and the dry coating film thickness t ₀
/ 0 μm at 0.70 to 0.90 (t ₀ is 1
00 to 300), and the color difference (ΔE) between the dried coating film having a desired thickness t ₀ μm applied to the outer plate surface of the anticorrosive coating composition and the outer plate surface is 100. When performing the coating, the color difference (ΔE) between the coating film in the wet state of the coating portion and the surface of the outer plate is observed, and the coating amount of the coating composition is controlled so that the color difference (ΔE) is 90 or more. Process,
And (B) a step of further applying a nonorganotin-based hydrolyzable antifouling paint on the coating film of the undercoat anticorrosive paint composition formed on the surface of the outer plate in the step (A). And

In the present invention, (A) 'the bottom of a ship
Primer is applied to the entire surface of the skin, including the
Anticorrosion paint (primer)
Is the desired dry film thickness t₀ Concealment ratio in μm is 0.94 or less
Less than 1 and dry film thickness t₀/ 2 μm
0.70 to 0.90 (t₀Becomes 100-300)
So that the anticorrosive coating composition is coated on the outer plate surface.
Desired thickness t₀μm dry coating film and outer plate surface
When the color difference (ΔE) is 100, the wet state of the painted part
Observe the color difference (ΔE) between the paint film in the dry state and the surface of the outer plate.
Applying the coating composition so that (ΔE) is 90 or more.
Controlling the amount of coating, and (B) '
In the step (A) ', the outer bottom plate (a) of the outer plates,
Is the bottom formed on the surface of the outer plate (b) at the bottom of the ship and the water line.
Non-organic tin-based water
How to paint a ship's skin including the step of applying a degradable antifouling paint
It may be a law.

In the present invention, (A) '
On the entire surface of the outer plate including the bottom, water line and outboard,
As the anti-corrosion paint (primer),
The product is dried to the desired dry film thickness t₀ 0.9 μm concealment ratio
4 or more and less than 1, and the dry coating thickness t₀/ 2μm concealment
The rate is 0.70 to 0.90 (t₀Is 100-300)
Adjusted so that the surface of the outer plate of the anticorrosive coating composition
Painted desired thickness t₀μm dry coating and outer plate surface
When the color difference (ΔE) with respect to
The color difference (ΔE) between the coating film in the
So that the color difference (ΔE) is 90 or more.
Coating by controlling the amount of application, and (B) '
In the step (A) ', the outer bottom plate (a) of the outer plates,
Is the bottom formed on the surface of the outer plate (b) at the bottom of the ship and the water line.
Non-organic tin-based water
Applying a degradable antifouling paint, and (C)
In the step (A) ', the outer surface of the outer plate
The outer coat is further formed on the formed undercoating anticorrosion coating composition coating film.
How to paint a ship's outer panel, including the step of applying a top coat
It may be a law. In addition, if necessary,
On the coating film of the undercoat anticorrosive coating composition formed on the surface of
Further, an overcoat for the water line portion may be applied.

A coated ship according to the present invention is obtained by the method for coating a ship outer plate according to the present invention, and includes a ship bottom outer plate.
(A) or having a primer layer formed on the surface of the outer plate (b) of the ship bottom and the water line part, and a non-organic tin-based hydrolyzable antifouling paint layer formed on the primer layer It is characterized by.

A coated ship according to the present invention is obtained by the method for coating a ship outer plate according to the present invention, and has a primer formed on the entire surface of the outer plate including a bottom portion, a water line portion and a port side portion of the ship. Layer and the bottom shell of the primer layer (a)
Or a non-organic tin-based hydrolyzable antifouling paint layer formed on the primer layer of the outer plate (b) of the ship bottom and the water line part.

Further, a coated ship according to the present invention is obtained by the method for coating a ship outer plate according to the present invention, and is formed on the entire surface of the outer plate including a bottom portion, a water line portion and a port portion of the ship. A non-organic tin-based hydrolyzable antifouling layer formed on the primer layer and the primer layer on the bottom plate of the primer layer (a) or the bottom plate and the water line portion of the outer plate (b) When,
And an outer coating layer formed on the primer layer of the outer panel. Further, on the primer layer formed on the surface of the water line part outer plate, a water line part top coating layer may be further formed.

According to the present invention, in any of the above coating methods and coating vessels, the anticorrosive coating composition or the primer layer formed by coating and curing the coating further comprises a thermoplastic resin and / or an ester plasticizer in an amount of 5 to 90%. It is preferred that the content be contained by weight.

The thermoplastic resin is one or more of an acrylic resin, a vinyl chloride-isobutyl vinyl ether copolymer, a coumarone indene resin, a xylene resin, and an ester group-containing pentadiene copolymer. Is preferred.

The light-transmitting inorganic filler is preferably a powder or a granular material of talc, mica, silica, potassium feldspar or barium sulfate. Further, it is preferable that the outer coating for outer periphery or the outer coating for outer coating formed by applying and curing the upper coating is a urethane type, an epoxy type, an acrylic type or a chlorinated polyolefin type (chlorinated rubber type). .

The water line part top coat or the water line part top coat layer formed by coating and curing the top coat is made of urethane, epoxy, acrylic, chlorinated polyolefin (chlorinated rubber) or non-organic. It is preferable to use a tin-based antifouling paint or a mixture of these paints.

According to the method of coating a ship outer panel according to the present invention, a single type of anticorrosive paint can be used for the outer panel portion of the ship (bottom portion, water line portion, and outer portion of the outboard portion) and the deck portion. Can,
In addition, it is possible to easily manage the thickness of the anticorrosion paint. In addition, it is possible to form a coating film with excellent anti-corrosion, weather resistance, and anti-fouling properties with a small variety of paints, thus shortening the painting period and reducing the cost of paint storage and storage. It is also effective in improving hygiene and protecting the environment.

Further, the coated ship according to the present invention is excellent in corrosion resistance, weather resistance and stain resistance because the primer layer comprising the anticorrosive coating composition has a uniform thickness.

[0026]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for coating a ship outer panel and a coated ship according to the present invention will be described in detail.

[0027] surface of the ship outside plate coating method of the present invention, the ship's bottom outer plate of the ship (a), or the outer plate of the ship's bottom portion and waterline of the ship (b), as a primer anticorrosive paint (primer), A bisphenol-type epoxy resin (non-tar epoxy resin) anticorrosion paint composition or a urethane resin anticorrosion paint composition as described below has a hiding factor of 0.94 or more and less than 1 at a desired dry coating film thickness t ₀ μm, preferably from 0.94 to 0.96, dry film thickness t _0/2
The concealment ratio in μm is 0.70 to 0.90, preferably 0.
70 to 0.85 (t ₀ is 100 to 300), and a dried coating film of a desired thickness t ₀ μm applied to the surface of the outer plate of the anticorrosive coating composition; When the color difference (ΔE) from the surface is set to 100, the color difference (ΔE) between the coating film in the wet state of the painted portion and the outer plate surface is observed, and the color difference (ΔE) is observed.
The coated amount of the anticorrosion coating composition is controlled so that E) is 90 or more, preferably dried, and then subjected to the primer treatment as described above (coating of the anticorrosion coating composition) Further, the following non-organic tin-based hydrolyzable antifouling paint is applied.

According to the anticorrosion coating composition used in the present invention, the hiding ratio of the dry coating film of the anticorrosion coating composition is determined by the type and content of the coloring pigment and the light-transmitting inorganic filler having a refractive index of 2 or less. Can be adjusted. In the present invention, since the content of the coloring pigment in the anticorrosion coating composition is significantly reduced and the hiding power is reduced, the
Alternatively, a change in the concealment ratio can be identified by a change in the film thickness smaller than 40 μm, and the concealment ratio at the dry coating film thickness t ₀ μm is adjusted to 0.94 or more and less than 1. The desired thickness (t ₀ μm) of the dried coating film of the anticorrosive coating composition is set to 100 to 100 μm.
The reason why the thickness is set to 300 μm is to secure heavy anticorrosion performance in a ship.

The color difference (ΔE) between the coating film in the wet state and the surface of the outer plate is usually 90 when the color difference (ΔE) between the standard color sample plate having the desired thickness and the surface of the outer plate, which is prepared in advance, is 90%.
It is performed by visually observing a color sample plate that is and a coating film in a wet state of a painted portion.
It can be performed directly, or can be performed using an optical measuring device or the like that can compare these color differences.

The above concealment ratio is determined according to JIS K 5400 7.2
It is measured according to the method of measuring the opacity. Further, in the present invention, the following bisphenol-type epoxy resin (non-tar epoxy resin) is applied as an undercoat anticorrosive paint (primer) on the entire surface of the outer plate including the bottom, the water line and the outer hull of the ship. The anticorrosion coating composition or the urethane resin coating composition is applied in the same manner as the above method, preferably dried, and then the hull bottom outer panel (a) of the primer-treated outer panels, or the hull bottom and the water line Outer plate (b)
The following non-organic tin-based hydrolyzable antifouling paint may be further applied on the primer coating film formed on the surface of the above.

The flat bottom of the bottom of the ship is located at the deepest part of the water of the ship and is relatively unsuitable for the growth of algae due to little incidence of sunlight. Below.

Therefore, for the flat bottom part, a non-organic tin-based hydrolyzable antifouling paint having excellent antifouling properties is not used, and a conventional antifouling paint which is inexpensive and economical (for example, chlorinated rubber) Antifouling paints, vinyl antifouling paints, acrylic antifouling paints, etc.)
Further, depending on the operating environment of the ship, it is possible not to apply the antifouling paint.

In the present invention, the outer side of the ship (the outer plate above the water line of the hull) which has been subjected to the primer treatment is exposed to strong sunlight and wind waves, and is required to have weather resistance. It is preferable to apply a lacquer, acrylic or chlorinated polyolefin (chlorinated rubber) paint, and it is particularly preferable to apply a urethane paint.

According to the present invention, the water line portion of the above-mentioned primer-treated ship is exposed to a severe environment which is subjected to a dry-humidity interaction between immersion in seawater and exposure to the air, so that weather resistance, water resistance, and further necessity are required. Accordingly, antifouling properties are required, and the following non-organic tin-based hydrolyzable antifouling paint or water line top coating is applied.

As the top coat for the water line part, it is preferable to use urethane-based, epoxy-based, acrylic-based, chlorinated polyolefin-based (chlorinated rubber-based) paints or non-organic tin-based antifouling paints, especially epoxy-based paints. Alternatively, it is preferable to use a non-organic tin-based hydrolyzable antifouling paint.

When the above-mentioned method is applied to the outer shell of a ship, (1) the surface of the entire outer shell including the bottom, the water line and the outer hull, which is the entire outer shell of the boat, After primer coating (preferably further drying),
(A) Alternatively, the primer layer formed on the surface of the outer plate (b) at both the ship bottom and the water line may be further coated with a non-organic tin-based hydrolyzable antifouling paint.

(2) Each part of the outer panel, ie, the outer panel at the bottom, the water line or the outer hull, is provided with a primer coating and a non-organic tin-based hydrolyzable antifouling paint (the bottom panel (a), Or top coat with outer plate (b) on the bottom of the ship and water line, or primer coating and top coat for the outer part (outer part) or top coat for the water line (water line). Further, a primer coating and a non-organic tin-based hydrolyzable antifouling paint (ship bottom shell (a), or shell bottom and water line shell)
(B)), or a primer coating and a top coat for the outer part (outside part) or a top coat for the water line part (water line part) may be applied.

In the present invention, the predetermined top coat may be applied sequentially from the outer plate after the primer coating is completed and dried. Hereinafter, first, an undercoat anticorrosion paint (bisphenol-type resin anticorrosion paint composition, urethane resin anticorrosion paint composition), a non-organic tin-based hydrolyzable antifouling paint, and a top coat for outer parts used in such a coating method. The paint and the overcoat for the water line part will be described.

Undercoat anticorrosion paint The undercoat anticorrosion paint (primer) used in the present invention is:
A bisphenol-type epoxy resin anticorrosion coating composition and a urethane resin anticorrosion coating composition.

[Bisphenol-type epoxy resin anticorrosion paint composition] The bisphenol-type epoxy resin anticorrosion paint composition used in the present invention is a heavy-duty anticorrosion paint, and comprises bisphenol-type epoxy resin, epoxy curing agent, coloring pigment, It contains a light-transmitting inorganic filler, and if necessary, may contain a thermoplastic resin, an ester-based plasticizer, and the like in addition to these components.

<Bisphenol Epoxy Resin> The bisphenol epoxy resin used in the present invention is a liquid or solid bisphenol epoxy resin having an epoxy equivalent of 150 to 1,000.

More specific examples of the epoxy resin include bisphenol A type and bisphenol F type epoxy resins, as well as dimer acid-modified and polysulfide-modified epoxy resins. A hydrogenated structure can also be used. Aromatic epoxy resins such as bisphenol A or bisphenol F type are preferred.

As a typical bisphenol-type epoxy resin, those which are liquid at room temperature include "Epicoat 828".
(Trade name) "(manufactured by Shell Co., Ltd., epoxy equivalent 180-
190, viscosity 12,000 to 15,000 cPs / 25
° C), "Epototo YDF-170 (trade name)" (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 160-180, viscosity 2,
000-5,000 cPs), “FLEP 60 (trade name)” (manufactured by Toray Thiokol Co., Ltd., epoxy equivalent: about 28
0, a viscosity of about 17,000 cPs / 25 ° C.), and a semi-solid type at room temperature, “Epototo YD-134 (trade name)” (manufactured by Toto Kasei Co., Ltd., epoxy equivalent 230 to 270) and the like, and in a solid state at normal temperature, “Epicoat 1001 (trade name)” (manufactured by Shell Co., Ltd., epoxy equivalent 450 to 50)
0).

<Curing Agent for Epoxy Resin> As the curing agent for epoxy resin used in the present invention, an amine-based curing agent comprising polyamideamine, polyamine or a modified product thereof capable of reacting and curing the above-mentioned bisphenol-type epoxy resin is used. preferable. In many cases, the coating of the ship's outer panel is performed under a normal temperature environment, and a curing agent that can be cured at normal temperature is preferably used.

As such an amine-based curing agent, a liquid or solid curing agent having an amine value of 50 to 1,000 is preferable. When these amine-based curing agents are exemplified in more detail, polyalkylene polyamines, aromatic amines, polyamidoamines and the like can be mentioned, and an epoxy adduct obtained by adding an epoxy compound to these amines,
Modified products such as Mannich modified product and amide modified product with carboxylic acid can also be used.

Further, ketimine type curing agents obtained by modifying these amine compounds with ketones can also be used. Among these curing agents, as the polyamide, specifically, “Lacamide TD-966 (trade name)”
(Dainippon Ink Chemical Industry Co., Ltd., amine value 150-1
Examples of other amine-based curing agents include epoxy resins such as "ancamine MCA (trade name)", a modified alicyclic polyamine of the ketimine type (anchor chemical company, amine value 250 to 350). Modified phenorcamine, such as "PA-23 (trade name)", which is an adduct-based amine (trade name, 80-150, manufactured by Otake Meishin Chemical Co., Ltd.), "Card Light 541LV (trade name)" (trade name, manufactured by Anchor Chemical Co., Ltd.) , Amine value 260-35
0) and various kinds of compounds such as "ADEKA HARDNER EH101 (trade name)" (manufactured by Asahi Denka Co., Ltd., amine value 400 to 500) which is a modified aromatic polyamine. Among these amine-based curing agents, an epoxy adduct of polyamidoamine and modified phenorcamine are particularly preferred.

<Coloring Pigment> The coloring pigment used in the present invention is a conventionally known coloring pigment for blending paints, excluding carbon black.

The coloring pigment is contained in the bisphenol-type epoxy resin anticorrosion coating composition (including a curing agent) in a proportion of 0.3 to 5% by weight, preferably 1.0 to 4.8% by weight in terms of solid content. It is contained.

Specific examples of the color pigment include white pigments such as titanium oxide, yellow pigments such as yellow lead, yellow petal and benzidine yellow; orange pigments such as red-mouthed graphite and chrome vermilion; Red pigments such as Red 4R, purple pigments such as cobalt violet, blue pigments such as ultramarine, phthalocyanine blue and cobalt blue, and green pigments such as phthalocyanine green, cobalt green and chrome green.

These pigments can be used alone or in combination of two or more. <Light-transmitting inorganic filler> Specific examples of the light-transmitting inorganic filler preferably used in the present invention include powders or granular materials such as talc, mica, silica, potassium feldspar, and barium sulfate. The average particle size of the light-transmitting inorganic filler is usually 0.05 to 80 μm, preferably 0.5 to 2 μm.
0 μm.

The light-transmitting inorganic filler is contained in the bisphenol-type epoxy resin anticorrosive coating composition (including a curing agent) in a volume concentration of 25 to 50% by volume, preferably 30 to 4% by volume.
It is contained at a rate of 0% by volume. This filler volume concentration is the volume percentage of the light-transmitting inorganic filler contained in the dried coating film.

<Thermoplastic resin> The bisphenol-type epoxy resin anticorrosion coating composition used in the present invention preferably further contains a thermoplastic resin in addition to the above-mentioned components. In this case, the thermoplastic resin is preferably blended in an amount of 5 to 90 parts by weight based on 100 parts by weight of the total amount of the bisphenol-type epoxy resin and the curing agent.

The thermoplastic resin acts as a moderator for internal stress when the bisphenol-type epoxy resin anticorrosion coating composition is cured, and serves as a base or undercoat coating layer and a primer layer formed by applying and curing the epoxy resin coating. The thermoplastic resin is soluble in a solvent and is swelled or dissolved by the solvent in the top coating, so that the adhesion of the primer layer to the top coating can be improved or the epoxy resin coating can be improved. Can be extended (relaxed), thereby contributing to the expansion of applicable types of various top coatings applicable on the primer layer.

As such a thermoplastic resin, specifically, a methyl (meth) acrylate-based copolymer, a (meth)
Acrylic resins such as ethyl acrylate copolymer, propyl (meth) acrylate copolymer, butyl (meth) acrylate copolymer, cyclohexyl (meth) acrylate copolymer; vinyl chloride-acetic acid Vinyl copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-
Vinyl chloride resins (PVC copolymers) such as isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, and vinyl chloride-ethyl vinyl ether copolymer; Coumarone indene resin; aromatic petroleum resins such as xylene resin Aliphatic petroleum resins; chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; styrene resins; urea aldehyde condensation resins; ketone resins; ester group-containing pentadiene copolymers. Among them, an acrylic resin, a vinyl chloride-isobutyl vinyl ether copolymer, a coumarone indene resin, a xylene resin, and an ester group-containing pentadiene copolymer are preferred. These can be used alone or in combination of two or more.

Examples of such a vinyl chloride-isobutyl vinyl ether copolymer include "Laroflex LR8829 (trade name)" and "Laloflex M" manufactured by BASF.
P25 (trade name) "," Laloflex MP35 (trade name) "," Laloflex MP45 (trade name) "and the like.

<Ester-based Plasticizer> The bisphenol-type epoxy resin anticorrosion coating composition used in the present invention preferably further contains an ester-based plasticizer in addition to the above-mentioned components. In this case, the ester plasticizer is
Total amount of bisphenol type epoxy resin and curing agent 100
It is preferred to be blended in an amount of 5 to 90 parts by weight with respect to parts by weight. An ester plasticizer can be used in combination with the thermoplastic resin.

The ester-based plasticizer acts as an internal stress relieving agent when the bisphenol-type epoxy resin anticorrosion coating composition is cured, and serves as a primer or undercoat coating layer and a primer layer formed by applying and curing the epoxy resin coating. This ester-based plasticizer is solvent-soluble and swells or dissolves with the solvent in the overcoat, so that the adhesion of the primer layer to the overcoat is improved, The coating interval limit of the resin coating can be extended (relaxed), and this contributes to the expansion of applicable types of various top coatings applicable on the primer layer.

As the ester plasticizer, specifically,
Phosphate esters such as tributyl phosphate, triphenyl phosphate and tricresyl phosphate; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate,
Phthalates such as diisononyl phthalate and diundecyl phthalate; aliphatic monobasic esters such as butyl oleate, isopropyl oleate and amyl oleate;
Examples include aliphatic dibasic acid esters such as dibutyl sebacate, diisooctyl sebacate, and dihexyl sebacate.

<Other Ingredients> The bisphenol-type epoxy resin anticorrosion coating composition contains various other solvents, curing accelerators, anti-sagging agents, anti-settling agents, and other materials commonly used in coatings. Is also good.

Such a bisphenol-type epoxy resin anticorrosion coating composition is usually composed of two components, a composition (I) containing an epoxy resin component and a composition (II) containing a curing agent component. The molds are stored in separate containers, respectively, and they are mixed and used at the time of application of the primer, or are mixed and used at the time of coating with a mixing sprayer such as a two-head gun.

In the case where a curing agent modified so as not to react with the epoxy resin component during storage (for example, a ketimine type amine block type curing agent) is used as the epoxy resin curing agent, bisphenol type epoxy resin anticorrosion is used. The coating composition can be used as a one-pack type.

In such a bisphenol-type epoxy resin anticorrosion coating composition, the epoxy resin component and the curing agent component are usually mixed (combined) at an equivalent ratio of 1: 0.1 to 1: 2.
Is preferably performed.

Since such a bisphenol-type epoxy resin anticorrosion coating composition is made of a non-tar epoxy resin, unlike a tar-based epoxy resin coating, skin irritation and irritation rarely occur during coating.

[Urethane Resin Anticorrosion Coating Composition] The urethane resin anticorrosion coating composition used in the present invention is a substantially fine solvent or solvent-free heavy anticorrosion coating, and contains polyol and / or polythiol and urethane resin. It contains a polyisocyanate-based curing agent, a coloring pigment, and a light-transmitting inorganic filler. If necessary, in addition to these components, a thermoplastic resin or the like may be contained.

<Polyol> Examples of the polyol used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, and diethylene glycol. Butylene glycol, tributylene glycol, polybutylene glycol, 1,5-pentanediol, neopentyl glycol,
Dihydric alcohols such as 1,6-hexanediol, 1,10-decanediol, alkanediol, and cyclohexanedimethanol; glycerol, trimethylolpropane (TM
P), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane,
1,1,1-tris (bishydroxymethyl) propane, 2,2-
Trihydric alcohols such as bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols (pentit) such as arabbit, ribitol and xylitol; sorbitol, mannitol, galactitol, allodulcit and the like Hexahydric alcohol (hexit); derived from polyglycol compounds having up to about 10 carbon atoms, such as polyhydric hydroxy compounds such as polyglycerol and polytetramethylene glycol; and phthalic anhydride, sebacic acid, fatty acids, epoxy resins and the like. Examples include polyester polyol, epoxy polyol (alkanolamine-modified epoxy), polyether polyol, and acrylic polyol.

Among them, ethylene glycol, propylene glycol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, polyester polyol and acrylic polyol are preferred.

<Polythiol> The polythiol (polymercapto compound) used in the present invention is a compound having two or more mercapto groups (—SH groups). As the polythiol, specifically, 1,3-propanedithiol,
1,4-butanedithiol, 1,6-hexanedithiol, 2,3-
Dimethylcaptopropanol, toluene-3,4-dithiol, α, α'-dimethylcapto-p-xylol, dimercaptoethane, diethylene glycol dimercaptan,
Triethylene glycol dimercaptan, dithiocatechol, 3-chlorothiocatechol, dithioresorcin, dimercaptotoluene, xylylene dimercaptan, 1,3,
5-trimercaptobenzene, dimercaptonaphthalene,
Zidodecanedithiol, dithiol phenol, 4,4'-
Dithiophenol, 2,2′-dimethyl-4,4′-thiodiphenol, dimercaptobenzothiazole, dithioerythritol and the like.

Further, specific examples of polythiols other than those described above include a complete ester or a partial ester comprising an aliphatic polyol and a mercapto lower fatty acid. As the aliphatic polyol, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol,
Dipropylene glycol, tripropylene glycol,
Polypropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,10-decanediol, alkanediol, cyclohexanedimethanol, etc. Glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl ) Trihydric alcohols such as propane and 2,2-bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols (pentits) such as arabbit, ribitol and xylitol; , Galactito And hexahydric alcohols (hexit) such as allozurcit. Among them, glycerol, trimethylolpropane, and pentaerythritol are preferred.

Glycidyl ethers such as bisphenol A glycidyl ether, hydrogenated bisphenol A glycidyl ether, bisphenol F glycidyl ether, and novolak epoxy can also be used.

Examples of the above mercapto lower fatty acids include mercaptoacetic acid, mercaptopropionic acid, mercaptosalicylic acid, mercaptoglycolic acid, N- (2-hydroxyethyl) thioglycolic acid, mercaptosuccinic acid, and mercaptomalic acid. And the like. Among them, mercaptoacetic acid (HSCH ₂ COOH),
Mercaptopropionic acid is preferred.

The polythiol particularly preferably used in the present invention is an ester having 2 to 4 mercapto groups consisting of pentaerythritol and mercaptoacetic acid or mercaptopropionic acid, or trimethylolpropane and mercaptoacetic acid or mercaptopropionic acid.

The thiol compound having one mercapto group can be used as a diluent or a plasticizer. In the present invention, it is not necessary to use a solvent, and it is desirable to use a polythiol having no or little odor.

<Polyisocyanate Curing Agent> Examples of the polyisocyanate used as the polyisocyanate curing agent in the present invention include hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI), 1,3-bis (Isocyanatomethyl) cyclohexane (hydrogenated XDI, H6 XDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4,4-bis (isocyanatocyclohexyl) methane (hydrogenated MDI), naphthylene diisocyanate (NDI) ), Isophorone diisocyanate (IP
DI), meta-xylylene diisocyanate (MXD
I), lysine diisocyanate (2,6-diisocyanatomethylcaproate) (LDI), methylcyclohexane-2,4 (or2,6) -diisocyanate (hydrogenated TDI or
HTDI), trimethylhexamethylene diisocyanate (TMDI), dimer acid diisocyanate (DD)
I), tolidine diisocyanate (TODI), p-phenylene diisocyanate, transcyclohexane-1,4
-Diisocyanates such as diisocyanate and tetramethyl xylene diisocyanate (TMXDI); triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate Triisocyanates such as 4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.

[0074] Nurates or adducts derived from the isocyanates described above can also be used as curing agents. Specific examples of the polyisocyanate other than the above include the following carbodiimide-type polyisocyanates. This carbodiimide-type polyisocyanate has one or more -N = C = N- groups, and specifically, carbodiimide-type diphenylmethane diisocyanate, carbodiimide-type tolylene diisocyanate, carbodiimide-type dimethylbiphenylene diisocyanate, carbodiimide-type xylylene diisocyanate, Carbodiimide-type naphthalene diisocyanate,
Examples include carbodiimide-type hexamethylene diisocyanate, carbodiimide-type isophorone diisocyanate, carbodiimide-type hydrogenated xylylene diisocyanate, and carbodiimide-type hydrogenated diphenylmethane diisocyanate.

The polyisocyanates preferably used in the present invention are carbodiimide-type diphenylmethane diisocyanate, carbodiimide-type tolylene diisocyanate, carbodiimide-type dimethylbiphenylene diisocyanate, and carbodiimide-type hexamethylene diisocyanate. Particularly, carbodiimide-type diphenylmethane diisocyanate is preferably used.

The carbodiimide type polyisocyanate having one —N ＝ C ＝ N— group can be represented by the following formula. ^{(OCN-R 1) -N =} C = N- (R 2 -NCO) [ in the formula ^{(OCN-R 1), (} R 2 -NCO) is a polyisocyanate. Further, specific examples of the polyisocyanate other than the above-mentioned polyisocyanate include (1) a trihydric or higher aliphatic polyhydric alcohol (i), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and meta-xylylene diisocyanate ( MXDI), an adduct with hexamethylene diisocyanate (HDI or HMDI), isophorone diisocyanate (IPDI), or bis (isocyanatomethyl) cyclohexane (ii), and
(2) Hexamethylene diisocyanate (HDI or HM
DI), isophorone diisocyanate (IPDI), or bis (isocyanatomethyl) cyclohexane of the following formula (I):

[0077]

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An isocyanurate structure having a ring (nurate structure) represented by the following formula: Specific examples of the trihydric or higher aliphatic polyhydric alcohol (i) used as a component of the adduct include glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, Trihydric alcohols such as 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane and 2,2-bis (hydroxymethyl) butanol-3; pentaerythritol, diglycerol, etc. Pentahydric alcohols (pentit) such as arabic, ribitol and xylitol; and hexahydric alcohols (hexit) such as sorbit, mannitol, galactitol, allozurcit and the like. Among them, trimethylolpropane and pentaerythritol are particularly preferred.

Further, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), metaxylylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), isophorone diisocyanate (IPDI), Among bis (isocyanatomethyl) cyclohexane (hydrogenated XDI, H6 XDI) (ii), 1,3-bis (isocyanatomethyl) cyclohexane, tolylene diisocyanate (TDI) and xylylene diisocyanate (XDI) are preferred.

The adduct (1) used in the present invention is obtained by addition polymerization of the above-mentioned trihydric or higher aliphatic polyhydric alcohol (i) with bis (isocyanatomethyl) cyclohexane or the like (ii). can get.

The adduct preferably used in the present invention includes, for example, compounds represented by the following formulas.

[0082]

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The isocyanurate structure (nurate structure) used as the polyisocyanate in the present invention has one or more rings represented by the above formula (I) in the molecule.

The isocyanurate structure used in the present invention may be, for example, the above-mentioned bis (isocyanatomethyl)
It can be obtained by performing a trimerization reaction, a pentamerization reaction, and a heptamerization reaction of cyclohexane (hydrogenated XDI, H6 XDI).

In the present invention, the components of the polyol and / or polythiol and the polyisocyanate contained in the urethane resin anticorrosive coating composition are equivalent to the isocyanate group equivalent contained in the polyisocyanate, the hydroxyl equivalent contained in the polyol and the polythiol equivalent. To the total amount of equivalents of thiol groups contained in [NCO group / (OH group +
SH group)] is usually 0.1 to 5, preferably 0.2 to 4,
More preferably from 0.5 to 3, particularly preferably from 0.7 to
It is used in an amount falling within the range of 2.

When a carbodiimide-type polyisocyanate as described above is used in combination with a polyisocyanate other than the carbodiimide-type isocyanate, the carbodiimide-type isocyanate is usually used in an amount of 100 parts by weight based on the total amount of these polyisocyanates. It is used in an amount of 1 part by weight to less than 200 parts by weight, preferably 5 parts by weight to less than 150 parts by weight, more preferably 20 parts by weight to less than 100 parts by weight.

When the carbodiimide-type polyisocyanate is used in the above amount, a polyurethane coating which can be rapidly cured to form a coating film can be obtained. The urethane resin anticorrosion coating composition containing the polyol and / or polythiol and the polyisocyanate as described above has a long pot life and is easy to handle.

<Coloring Pigment> The coloring pigment used in the present invention is a conventionally known coloring pigment for blending a coating material, excluding carbon black, and is the same as the above-mentioned coloring pigment constituting the bisphenol-type epoxy resin anticorrosion coating composition. It is.

The coloring pigment is contained in the urethane resin anticorrosion coating composition (including the curing agent) at a ratio of 0.3 to 5% by weight, preferably 1.0 to 4.8% by weight in terms of solid content. ing.

<Light-transmitting inorganic filler> The light-transmitting inorganic filler used in the present invention is the same as the light-transmitting inorganic filler constituting the bisphenol-type epoxy resin anticorrosion coating composition described above.

The light-transmitting inorganic filler is contained in the urethane resin anticorrosive coating composition (including the curing agent) in an amount of 25 to 50% by volume.
(Filler volume concentration), preferably 30 to 40% by volume.

<Thermoplastic Resin> The urethane resin anticorrosive coating composition used in the present invention preferably further contains a thermoplastic resin in addition to the above-mentioned components. This thermoplastic resin is the same as the above-mentioned thermoplastic resin which may constitute the bisphenol-type epoxy resin anticorrosion coating composition. This thermoplastic resin is 5 to 9 parts by weight based on 100 parts by weight of the total amount of the urethane resin and the isocyanate-based curing agent.
Preferably, it is blended in an amount of 0 parts by weight.

The thermoplastic resin acts as a moderator for internal stress when the urethane resin anticorrosive coating composition is cured,
Improves the adhesion between the undercoat or undercoat layer and the primer layer formed by applying and curing the urethane resin paint, and the thermoplastic resin is solvent-soluble and swells or is dissolved by the solvent in the topcoat paint. Therefore, it is possible to improve the adhesion of the primer layer to the top coating and extend (relax) the coating interval restriction of the urethane resin coating,
This contributes to the expansion of applicable types of various top coatings that can be applied on the primer layer.

<Ester Plasticizer> The urethane resin anticorrosion coating composition used in the present invention preferably further contains an ester plasticizer in addition to the above-mentioned components.
This ester-based plasticizer is the same as the ester-based plasticizer that may constitute the above-described bisphenol-type epoxy resin anticorrosion coating composition. This ester-based plasticizer has a total amount of urethane resin and polyisocyanate-based curing agent of 10%.
It is preferred to be blended in an amount of 5 to 90 parts by weight with respect to 0 parts by weight. An ester plasticizer can be used in combination with the thermoplastic resin.

The ester-based plasticizer acts as an internal stress relieving agent when the urethane resin anticorrosion coating composition is cured, and forms an undercoating or undercoating layer with a primer layer formed by applying and curing the urethane resin coating. Improve the adhesion, the ester-based plasticizer is solvent-soluble, because it is swelled or dissolved by the solvent in the overcoat, improving the adhesion of the primer layer to the overcoat,
The coating interval limit of the urethane resin paint can be extended (relaxed), which contributes to the expansion of applicable types of various top coats that can be applied on the primer layer.

<Other Components> In the urethane resin anticorrosion coating composition, various other solvents, curing accelerators, anti-sagging agents,
Various materials usually used for paints, such as an anti-settling agent, may be blended.

Such a urethane resin anticorrosion coating composition is usually composed of a composition (I) containing a polyol and / or a polythiol component and a composition (II) containing a polyisocyanate-based curing agent component. These are stored in separate containers as a two-pack type, and they are used as a mixture at the time of application of the primer, or are used at the time of coating by a mixing sprayer such as a two-head gun.

Non-organic tin-based hydrolyzable antifouling paint The non-organic tin-based hydrolyzable antifouling paint used in the present invention includes (i) a trialkylsilyl ester copolymer, and (ii)
A resin in which an organic acid is bonded to at least one side chain terminal of a vinyl resin through a metal ester bond, for example, a copper ester bond, for example, a copolymer containing an unsaturated carboxylic acid copper salt component, (iii) (meth) acrylic acid Paints containing a polymerizable unsaturated zinc carboxylate salt component-containing copolymer such as a hydroxyzinc copolymer or a zinc-free (meth) acrylate-free zinc-bonded (meth) acrylate-bonded copolymer are exemplified.

Among these, the trialkylsilyl ester copolymer (i), vinyl resin (ii) and copolymer containing a polymerizable unsaturated zinc carboxylate component (iii) preferably used in the present invention are described. Further details will be given.

<Trialkylsilyl ester copolymer>
(i)> This trialkylsilyl ester copolymer has a component unit derived from a trialkylsilyl ester of a polymerizable unsaturated carboxylic acid in an amount of 20 to 65% by weight and has a number average molecular weight (Mn) of 1,000. ~ 50,000.

The trialkylsilyl ester has, for example, the following formula (II):

[0102]

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Is represented by In this formula (II), R ¹ is
Represents an alkyl group such as a hydrogen atom or a methyl group,
R ² , R ³ and R ⁴ represent an alkyl group having about 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and the like, and R ² , R ³ and R ⁴ are different from each other. Or the same. Specific examples of such a trialkylsilyl ester include, for example,
R ² and R such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tributylsilyl (meth) acrylate, etc.
³ and R ⁴ are the same trialkylsilyl ester,
(Meth) acrylic acid dimethylpropylsilyl ester,
Trialkylsilyl esters in which one or all of R ² , R ³ and R ⁴ are different from each other, such as (meth) acrylic acid monomethyldipropylsilyl ester, (meth) acrylic acid methylethylpropylsilyl ester, etc. No.

In the present invention, such trialkylsilyl esters may be used alone or in combination of two or more. Among such trialkylsilyl esters, it is preferable that at least one alkyl group of R ² , R ³ and R ⁴ has 3 or more carbon atoms. Those having 3 or more atoms are preferred,
It is preferable that the total number of carbon atoms of R ² , R ³ and R ⁴ is about 5 to 21. Among such trialkylsilyl esters, in particular, ease of synthesizing the trialkylsilyl ester, or film-forming properties, storage stability, and scavenging properties of the antifouling paint composition using such a trialkylsilyl ester Considering the ease of control of
Most preferably, tributylsilyl acrylate or triisopropylsilyl ester copolymer is used.

As a monomer (comonomer) copolymerized with such a trialkylsilyl ester, any polymerizable unsaturated compound (ethylenically unsaturated monomer) can be used. As the saturated compound, specifically, for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid ethyl ester
Alkyl (meth) acrylates such as 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, and methoxyethyl (meth) acrylate; styrenes such as styrene and α-methylstyrene; vinyl acetate; and vinyl propionate And the like, and preferably, methyl methacrylate (MMA) is used. Such MMA is preferably contained in the comonomer (ethylenically unsaturated monomer) in an amount of usually 30% by weight or more, preferably 50% by weight or more.

In the copolymer, a component unit derived from a polymerizable unsaturated compound such as an alkyl (meth) acrylate and a component unit derived from a trialkylsilyl ester are used as raw materials in a copolymer. The ethylene bond of each of the monomers used is cleaved and usually bonds at random.

In such a film-forming copolymer, as described above, one or more component units derived from the above-mentioned trialkylsilyl ester of a polymerizable unsaturated carboxylic acid (tri- Alkyl silyl ester component unit), and such a trialkylsilyl ester component unit is contained in the copolymer in an amount of 20 to 65% by weight, preferably 30 to 55% by weight. It is preferable for the antifouling coating composition to contain an antifouling coating film having excellent long-term antifouling properties.

The number average molecular weight (Mn) of this copolymer measured by GPC is 1,000 to 50,000, preferably 2,000 to 20,000, and more preferably 2,500.
To 15,000, particularly preferably 3000 to 12000, and the weight average molecular weight (Mw) is usually 1000 to 15,000.
The molecular weight distribution (Mw / Mn) of the copolymer is desirably 150,000, preferably 2000 to 60000, and more preferably 3000 to 30000.
Usually, it is desirable to be 1.0-4.0, preferably 1.0-3.0, particularly preferably 1.0-2.5. The glass transition temperature (Tg) of the copolymer is usually 15 to
80 ° C, preferably 25 to 80 ° C, more preferably 3
The copolymer preferably has a viscosity (25 ° C.) of, for example, a 50% xylene solution of 30 to 1000 cP.
s, preferably 40 to 600 cPs.

To prepare such a film-forming copolymer, for example, a trialkylsilyl ester such as tributylsilyl methacrylate and a comonomer are usually added under an inert atmosphere such as a nitrogen stream in an organic solvent such as xylene. 50% by weight or more of methyl methacrylate (eg, 80
% By weight) and a polymerizable unsaturated compound contained in an amount of 2,
In the presence of a polymerization initiator such as an azo type or a peroxide type such as 2′-azobisisobutyronitrile and, if necessary, a polymerization regulator such as n-octyl mercaptan, 2-12
The reaction may be carried out by a method such as radical polymerization at a temperature of about 50 to 120 ° C. for about an hour.

The film-forming copolymer thus obtained contains each component unit in an amount corresponding to the amount of each monomer used. <Vinyl-based resin (ii)> The vinyl-based resin (ii) preferably contained in the non-organic tin-based hydrolyzable antifouling paint according to the present invention is an organic resin having a metal ester bond at least at one side chain terminal. It is a vinyl resin to which an acid is bonded.

Examples of such a vinyl resin (ii) include JP-A-8-73536, JP-B-7-108927, JP-B-7-68458, and JP-B-7-649.
No. 85, etc. can be mentioned.

The vinyl resin (ii) is, for example,
As described in JP-A-8-73536,
The alcohol residue of the ester is a branched alkyl group having 4 or more carbon atoms or a cycloalkyl group having 6 or more carbon atoms having at least one side chain on the second to fourth carbon atoms from the main chain terminal (meth) An acrylic acid ester (a), a polymerizable unsaturated organic acid monomer (b), and a neutral polymerizable unsaturated monomer (c) are copolymerized to synthesize a base resin. acid (example: -COOH, -SO ₃ H), a metal oxide,
Metal compounds such as hydroxides, chlorides, sulfides and the like, and a monobasic organic acid (eg, acetic acid, naphthenic acid) which is an organic acid are simultaneously reacted or the base resin is reacted with a monobasic organic acid. It can be produced by reacting a metal salt.

Examples of the (meth) acrylate (a) include t-butyl (meth) acrylate and (meth) acrylate.
Examples of the polymerizable organic acid monomer (b) include (meth) acrylic acid, maleic acid, and p-styrenesulfonic acid, and a neutral polymerizable unsaturated monomer. As the body (c), for example, ethylene,
Examples thereof include methyl (meth) acrylate and ethyl (meth) acrylate. As the metal constituting the metal compound, a metal having two or more valences, for example, Cu, Zn, Mn, Ca,
Fe, Al, Te, Ba and the like can be mentioned.

<Polymerizable unsaturated carboxylic acid zinc salt component-containing copolymer (iii)> The polymerizable unsaturated zinc carboxylate component-containing polymer (iii) includes (a) hydroxyzinc (meth) acrylate. A salt copolymer and (b) a hydroxy group-free zinc (meth) acrylate salt-based copolymer bonded to a metal atom are preferably used.

This (meth) acrylic acid hydroxyzinc salt-based copolymer (hydroxyzinc (meth) acrylate-based copolymer) (a) has a long-term slightly water-soluble property as a vehicle component and has a long-term antifouling property on a coating film. The (meth) acrylic acid hydroxyzinc salt-based copolymer includes:
JP-A-8-209005, JP-A-9-28693
No. 3, Rp-COOZn-OH ... [II] (wherein Rp represents a base resin in the formula [II]) Preferably, the resin [II] has the following formula:

Thus, the hydroxyzinc (meth) acrylate copolymer represented by the formula [II] as the resin [II] having a carboxyl group in the molecule is a resin having a carboxyl group in the molecule. By reacting a divalent zinc oxide or hydroxide in the presence of a small amount of water.

In such a reaction, zinc oxide or hydroxide is used in an amount of 0.1 to 1 mol based on 1 mol of the carboxyl group in the resin, and water is added to the carboxyl group. It is used in an amount of 0.1 to 1 mol based on 1 mol of the group.

As a more specific method for synthesizing the resin [II], as described in JP-A-9-286933, a resin having a carboxyl group in the molecule may be used in an amount of 0.5 to 0.5%. 5% by weight of water and a divalent zinc oxide or hydroxide to be added, and if necessary, a very small amount of a polar solvent for preventing turbidity,
The reaction may be performed at a temperature of 200C for 1-20 hours.

The resin having a carboxyl group in the molecule is preferably a carboxyl group-containing monomer such as (meth) acrylic acid and an alkyl acrylate (for example,
A vinyl polymer obtained by copolymerizing another vinyl monomer such as methyl methacrylate or ethyl acrylate) or styrene is used. As long as it contains a carboxyl group, various other vinyl polymers, polyesters,
Polyurethane, natural resin and the like can also be used.

As the polar solvent, alcohols such as butanol, ketones, esters and ethers are used. The number average molecular weight of the (meth) acrylic acid hydroxyzinc salt-based copolymer thus obtained is usually
1,000-50,000, preferably 3,000-2
And a glass transition temperature (Tg) of -10.
C. to + 60.degree. C., preferably +10 to + 40.degree. C., and the acid value is 80 to 200.

The hydroxyzinc (meth) acrylate copolymer (a) is used in the antifouling paint composition in an amount of usually 1 to 99% by weight, preferably 10 to 70% by weight as a resin component. Is preferably included. If the (meth) acrylic acid hydroxyzinc salt-based copolymer is contained in the antifouling coating composition in the range of 1 to 99% by weight, and more preferably 10 to 70% by weight, the coating film surface will be prolonged. Over a long period of time and tend to have excellent antifouling properties.

The zinc (meth) acrylate-based copolymer (b) containing no hydroxy group bonded to a zinc atom used in the present invention has a long-term slight water solubility as a vehicle component and has It has a function of imparting antifouling properties, and this (meth) acrylate zinc salt-based copolymer is disclosed in
No. 171066, a zinc (meth) acrylate (a) of a polymerizable monomer and a monomer having a hydroxyl group and / or an amino group copolymerizable with the zinc (meth) acrylate. (B) and these monomers
(A) and (B) are copolymerized with "another monomer" (C) copolymerizable with (B), and the component unit derived from zinc (meth) acrylate (A) usually has 2 to 30 units. % By weight, 2 to 30% by weight of the component unit derived from the monomer (b) having a hydroxyl group and / or amino group, and the remaining amount of the component unit derived from the other monomer (c), that is, 40 to 40%. 96% by weight ((a) + (b) + (c)
Is 100% by weight).

Specific examples of such a zinc (meth) acrylate include zinc methacrylate: [(CH ₂ ＝
_{C (CH 3) -COO-) 2} Zn], zinc acrylate:
[(CH ₂ ＣＨCH—COO—) ₂ Zn] and the like.

As the vinyl monomer having a hydroxyl group and / or an amino group (b), as long as it has at least one of a hydroxyl group and an amino group, it may be 2 to 2 even if it is a monomer. It may be a trimer, and specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate And the like having one hydroxyl group. Other adducts of 2-hydroxyethyl (meth) acrylate with ethylene oxide, propylene oxide, γ-butyl lactone, ε-caprolactone, etc .; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Dimer; a monomer having a plurality of hydroxyl groups such as glycerol (meth) acrylate;

The monomer having an amino group may be any of primary to tertiary, and includes primary and secondary amino groups such as (meth) acrylamide and butylaminoethyl (meth) acrylate. Containing monomer; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate,
Examples thereof include dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, and dimethylaminopropyl (meth) acrylamide. Other examples include heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole.

The “other monomer” (c) copolymerizable with at least one of the above-mentioned zinc (meth) acrylate (a) and monomer (b) includes aliphatic, alicyclic Tribe,
Any of aromatic compounds may be used. Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i -Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate And aliphatic monomers such as glycidyl (meth) acrylate; alicyclic monomers such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; phenyl (meth) acrylate and benzyl (meth) acrylate And the like.

In addition, carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid and succinic acid, and esters derived from these carboxylic acids; styrene,
Vinyl toluene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, vinyl propionate and the like.

These monomers (a), (b) and (c) can be used alone or in combination of two or more. The number average molecular weight of the (meth) acrylic acid zinc salt-based copolymer obtained by copolymerizing such monomers (a), (b) and (c) is usually about 5,000 to 100,000. Yes, the glass transition temperature (Tg) is about −20 ° C. to + 50 ° C.

The zinc (meth) acrylate-based copolymer
(b) is usually contained as a resin component in the antifouling coating composition.
It is preferably present in an amount of up to 99% by weight, preferably 10 to 70% by weight. When this (meth) acrylic acid zinc salt-based copolymer is contained in the antifouling coating composition within this range, the surface of the coating film tends to have stable long-term wear and antifouling properties.

In order to produce such a zinc (meth) acrylate copolymer, the method described in JP-A-5-171066 may be used. For example, each component unit in the copolymer may be used. A corresponding amount of the zinc (meth) acrylate (a), a monomer (b) having a hydroxyl group and / or an amino group, and a copolymerizable with these monomers (a) and (b) The "other monomer" (c) may be mixed with an organic solvent such as toluene and subjected to solution polymerization or the like at a temperature of 60 to 180C for 5 to 14 hours in the presence of a radical polymerization initiator.

Outer coatings for outer part The outer coatings for outer part include oily (alkyd) type paints.
Phthalic acid resin, chlorinated polyolefin (chlorinated rubber), vinyl, acrylic, epoxy, urethane, silicone alkyd, acrylic silicone,
A top coating such as a fluororesin-based coating can be used.

[0132] The overcoat for the outboard part used in the present invention may be a urethane-based, epoxy-based, acrylic-based or chlorinated polyolefin-based (chlorinated rubber-based) paint in consideration of weather resistance, adhesion, economy and the like. As such a top coat for the outer part, “Unimarine (trade name)” (manufactured by Chugoku Paint Co., Ltd., isocyanate cross-linkable two-pack type urethane resin-based top coat), “Epicon Marine top coat” (Trade name), "Epicon Marine HB (trade name)" (China Paint Co., Ltd., modified polyamidoamine cross-linked two-pack type epoxy resin-based top coat), "Ravacs top coat (trade name)" (China paint ( Co., Ltd., chlorinated polyolefin-based top coating), "Acry 700 Top Coating (trade name)" (China Paint Co., Ltd., acrylic resin-based top coating) and the like.

Waterline Topcoat As the waterline topcoat, the various paints mentioned in the above-mentioned outer part topcoat can be used.
Non-organic tin antifouling paints can also be used.

In a harsh environment of alternating dry and wet conditions, such as a ship's outer panel, in which water immersion and air exposure are repeated due to ups and downs of the ship, water resistance, weather resistance, corrosion resistance and, if necessary, antifouling properties are required. Therefore, among these, it is preferable to use urethane-based, epoxy-based, acrylic-based, chlorinated polyolefin-based (chlorinated rubber-based) paints, or non-organic tin-based antifouling paints.

Examples of the overcoating material for the water line portion include an isocyanate crosslinking type two-component type urethane resin-based overcoating material “Unimarine (trade name)” (manufactured by Chugoku Paints Co., Ltd.) and a modified polyamidoamine crosslinking type two-packing type Epicon Marine Topcoat (Epicon Marine Topcoat (trade name)) (China Paint Co., Ltd.)
Co., Ltd.), "Epicon Marine HB (trade name)" (China Paint Co., Ltd.), chlorinated polyolefin-based top coating "Rabacs Top Coat (trade name)" (China Paint Co., Ltd.), acrylic resin top coat "Acry 700 Topcoat (Product Name)"
(Manufactured by China Paint Co., Ltd.).

Each of the above-mentioned paints used in the present invention includes components which are usually blended in ship exterior paints, such as antifouling agents, plasticizers, hydrolysis regulators, pigments, solvents, viscosity regulators, and the like. Other additives and the like may be included.

In the present invention, in order to form a coating film (cured film) formed by applying and curing each paint such as the above-mentioned primer on the outer plate surface of a ship, for example, airless spray, air spray, brush coating, A conventional method such as roller coating may be used. Prior to the primer treatment, if necessary,
Rust, oil, water, dust, slime, salt, etc. attached to the outer plate surface may be cleaned and removed. Also, the paint is
It may be diluted with a thinner or the like to an appropriate concentration before use.

The amount of such a paint to be applied varies depending on the type of ship, the type and combination of paints to be applied, etc., and is not determined unconditionally. Epoxy resin anticorrosion coating composition or urethane resin anticorrosion coating composition (primer)
Is, for example, in an amount of 150 to 800 g / m ² ,
It is applied to a thickness of about 00 μm, and its dry film thickness is 100 to
Non-organic tin-based hydrolyzable antifouling paint which is about 300 μm and is applied on the primer layer of the bottom of the hull outer panel and the water line, for example, in an amount of 200 to 800 g / m ² ,
It is applied to a thickness of about 50 to 500 μm, and its dry film thickness is
The urethane paint having a thickness of about 30 to 300 μm and applied on the primer layer on the outer side of the ship outer panel is, for example, 50 μm.
In an amount of to 300 g / m ^2, is applied about 40~300μm thickness, its dry film thickness is about 30 to 150 [mu] m.

At the time of airless spraying, for example,
The primary (air) pressure: about 4 to 8 kgf / cm ² , the secondary (paint) pressure: about 100 to 180 kgf / cm ² , and the coating conditions may be set at a gun moving speed of about 50 to 120 cm / sec.

The number of coatings of each of the above-mentioned paints is not particularly limited, and can be appropriately set according to the paint concentration, the required film thickness, etc., and may be once or plural times, respectively. Ships (painted vessels) obtained by coating and curing each paint so as to have the above-mentioned film thickness include metal vessels such as tankers, cargo ships, passenger ships, fishing boats, barges, and floating docks. Can be

Further, in the present invention, a bisphenol-type epoxy resin anticorrosion paint composition or a urethane resin anticorrosion paint composition excellent in various overcoating properties can be prepared by using, for example, an exposed portion (deck portion) other than an outer plate, an upper structure portion (upper structure). Parts, housings), hold parts, and ballast tank parts, it is possible to greatly reduce the paint variety of the entire ship.

In the present invention, the same primer for undercoating is uniformly applied to the exposed portion (deck portion), the upper structure portion (housing portion), the hold portion, and the ballast tank portion in addition to the outer plate as described above. In addition, the effect of the present invention can be further expected by unifying and coating the same top coat primer.

[0143]

According to the method for coating a ship outer panel according to the present invention, a single type of anticorrosive paint is used for the outer panel portion of the ship (bottom portion, water line portion and outer side portion) and the deck portion. It is possible,
In addition, it becomes easy to control the thickness of the anticorrosion paint. Further, in the method for coating a ship outer panel according to the present invention, a bisphenol-type epoxy resin anticorrosion paint or urethane resin anticorrosion paint composition, which is an integrated small variety of paints, and a non-organic tin-based hydrolyzable antifouling paint. It can be used to form a coating film with excellent antifouling properties, thus shortening the painting period and reducing paint storage and storage costs. It is also effective in improving the hygiene of paint workers and protecting the environment. It is. In addition, ships painted in this way, especially their outer panels, have excellent corrosion protection.

[0144]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

In the following examples, the film thickness (μm)
Is represented by a dry film thickness unless otherwise contradicted. In addition, the amounts of each component in the table are indicated by “parts by weight” unless otherwise specified.

Table 1 shows each component of the anticorrosion paint used in the present invention.

[0147]

[Table 1]

[Production Example of Non-tar Epoxy Resin Anticorrosion Paint] Main agent (composition containing epoxy resin) and curing agent (composition containing curing agent component) of non-tar epoxy resin anticorrosion paint having the composition shown in Table 2 Product).

In producing the non-tar epoxy resin anticorrosion paint having the composition shown in Table 2, the main ingredient was prepared by sufficiently dispersing the composition with a paint shaker using glass beads, and the curing agent was used. The mixture was uniformly mixed using a high-speed disper.

When applying the non-tar epoxy resin anticorrosive paint, the main agent and the curing agent were mixed at the weight ratios shown in Table 2 and immediately applied.

[0151]

[Table 2]

[Hiding Properties of Anticorrosion Paint] The above anticorrosion paints (K-1 to K-3, H-2 and H-3) were applied to a sandblasted 70 × 150 × 2.3 mm steel sheet by various dry films. Paint using air spray to obtain thickness,
After drying at 20 ° C. for 24 hours, various test plates were obtained.

With respect to the obtained test plate, the base concealment ratio depending on the coating film thickness was visually evaluated, and the color difference (ΔE) was measured. The color difference (ΔE) was measured using a test plate in which the substrate was completely concealed as a standard and using a spectral colorimetric method (JIS K 5400,
(According to 7.4.2). Table 3 shows the results. FIG. 1 shows the relationship between the dry film thickness and the concealment ratio.
FIG. 2 shows the relationship between the dry film thickness and the color difference (ΔE).

The evaluation criteria are as follows. <Evaluation Criteria> 5... ΔE ≦ 1.2 (sufficiently concealed) 4. <And ≦ 6 (slightly concealed) 2... ΔE is 6 <and ≦ 9 (transparent) 1... ΔE is 9 <(very transparent)

[0155]

[Table 3]

[0156]

[Table 4]

[Discoloration Resistance Test of Top Coating Film] Non-tar epoxy resin anticorrosion paint (primer) to be used on one side of a sandblasted 70 × 150 × 2.3 mm steel plate
Is coated with an air spray to a dry film thickness of 200 μm, dried at 20 ° C. for 24 hours, and then coated with a white chlorinated polyolefin-based overcoat (trade name: Lavacs overcoat white, manufactured by China Paint Co., Ltd.). Was applied using an air spray and dried at 20 ° C. for 24 hours to obtain a test plate. An outdoor exposure table (JIS K5400) in which the test plate was installed at the Ohtake Research Center of Chugoku Paint Co., Ltd. in Otake City, Hiroshima Prefecture so that the painted surface of the test paint on the test plate was on the front.
9.9), and after 30 days of outdoor exposure, the degree of discoloration of the top coat was visually evaluated.

Table 4 shows the results.

[0159]

[Table 5]

[Anticorrosion Test] Sandblasted 7
The test paint was applied to a steel plate of 0 × 150 × 2.3 mm using an air spray so that the dry film thickness became 200 μm, and dried at 20 ° C. for 7 days to obtain a test plate.

This test plate was placed in a 3% saline solution at 40 ° C. for 180 minutes.
Immersion for several days and adjust the degree of blister to ASTM D 714-5
6. The degree of rusting was visually evaluated according to ASTM D 610-85, and the adhesion was evaluated by the cross-cut tape method (JIS K5).
400, 8.5.2). Table 5 shows the results. <Evaluation score of blister test> 10 points: no blister 9 points: 0.5 mm diameter blister is 0.2 of the total area of test plate
8 points: 0.5 mm diameter blisters are 0.5% of the total area of the test plate
7 points: 0.5 to 1 mm diameter blisters are about 0.5% of the total area of the test plate 6 points: 1 to 2 mm diameter blisters are 0. 0% of the total area of the test plate
5 to 1% 5 points: 2 to 3 mm diameter blisters are 1 to 1 of the total area of the test plate
About 5% 4 points: 3-5mm diameter blisters are 5-5 of the total area of the test plate
About 10% 3 points: 3 to 5 mm diameter blisters are 10% of the total area of the test plate.
Approx. 15% 2 points: 3 to 5 mm diameter blisters are 15% of the total area of the test plate.
Approx. 30% 1 point: The blister generation area is 30% or more of the total area of the test plate

<Rating Test Evaluation Score (ASTM D61)
0-85)> 10 points: no rust to rusting area is 0.03 of the total area of the test plate
9%: Rust area is 0.03% or more of the total area of the test plate.
Less than 1% 8 points: Rust area is 0.1% or more of the total area of test plate 0.3
7 points: Rust area is 0.3% or more and less than 1% of the total area of the test plate 6 points: Rust area is 1% or more and less than 3% of the total area of the test plate 5 points: Rust area is tested 3% or more and less than 10% of the total area of the plate 4 points: Rust area is 10% or more and less than 16% of the total area of the test plate 3 points: Rust area is 16% or more and less than 33% of the total area of the test plate 2 Point: Rust area is 33% or more and less than 50% of the total area of the test plate 1 point: Rust area is 50% or more of the total area of the test plate

<Evaluation score of cross cut test> 10 points: Each cut is thin and smooth on both sides, and there is no peeling at every intersection of the cut and the square. 9 points: Cuts are slightly thicker. Eight points: There was slight peeling at the intersection of the cuts, and there was no peeling at a glance of the square, and the area of the defective portion was within 5% of the area of the entire square. 7 points: Peeling was found on both sides of the cut and at the intersection, and the area of the defect was within 5% of the total square area. 6 points: Peeling was found on both sides of the cut and the intersection, and the area of the defective portion was 5 to 15% of the total square area. 5 points: The width of peeling due to cuts is wider than “6 points”, and the area of the defective portion is 15 to 25% of the area of the entire square. 4 points: The width of the peeling due to the cut is wide, and the area of the defective portion is 25 to 35% of the total square area. 3 points: Each square was peeled at a glance, and its area was within 35% of the total square area. 2 points: Peeling due to cuts is larger than “3 points”, and the area of the defective portion is 35 to 50% of the area of the entire square. 1 point: Peeling due to cuts is larger than "2 points", and its area is 50 to 70% of the total square area. 0 point: The area of peeling is 70% or more of the area of all squares.

[0164]

[Table 6]

[Overcoat property test] (Adhesion test with various overcoat paints) A spray paint was applied to a sandblasted 70 × 150 × 2.3 mm steel plate so that the dry paint film thickness was 200 μm. After the application, an outdoor exposure table (JIS) was installed at Otake Research Center, China Paint Co., Ltd. in Otake City, Hiroshima Prefecture.
K5400 9.9) in accordance with Table 9 with the painted surface of the test paint exposed to the outside.
Each of the overcoat paints shown in the table was applied using an air spray so that the dry film thickness became 50 μm, and dried at 20 ° C. for 7 days to obtain a test plate.

After the test plate was immersed in a 3% saline solution at 20 ° C. for 90 days, the adhesion to various overcoat paints was evaluated by the cross-cut tape method (based on JIS K 5400 8.5.2.). Table 6 shows the evaluation results.

[0167]

[Table 7]

* 1: Chlorinated polyolefin-based top coat (one-pack type) manufactured by China Paint Co., Ltd. * 2: Isocyanate cross-linked two-pack type urethane-based top coat manufactured by China Paint Co., Ltd. * 3: China paint ( Co., Ltd., modified polyamidoamine crosslinked type two-pack type epoxy topcoat

[Brief description of the drawings]

FIG. 1 shows the relationship between the thickness of a dried coating film and the concealment ratio in Examples and the like of the present invention.

FIG. 2 shows a relationship between a dry coating film thickness and a color difference (ΔE) in Examples of the present invention and the like.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Itsuo Inoue 1-7, Meiji-Shinkai, Otake City, Hiroshima Prefecture F-term in China Paint Co., Ltd. 4D075 AE03 CA33 DA06 DB02 DC08 EA05 EA41 EB15 EB22 EB33 EB38 EB45 EB55 EC03 EC04 EC07 EC08 EC11 EC13 EC54 4J038 DB061 DG052 DG092 DG142 DG262 GA07 GA13 HA446 HA536 HA546 JB04 JB05 JB07 KA03 KA08 NA03 PA07 PB07

Claims (14)

[Claims] (A) An undercoating anticorrosive paint (primer) is applied on the surface of the outer shell (a) of the bottom of the ship or the outer shell (b) of the bottom and the water line part. (Ii) a curing agent for an epoxy resin comprising a polyamidoamine, a polyamine or a modified product thereof, (iii) a coloring pigment of 0.3 to 5% by weight (solid content), and (iv) light. Anticorrosion coating composition containing 25-50% by volume (filler volume concentration) of permeable inorganic filler, or (v) polyol and / or polythiol, (vi) polyisocyanate-based curing agent, (iii) coloring pigment An anticorrosive coating composition containing 0.3 to 5% by weight (solid content) and (iv) 25 to 50% by volume (filler volume concentration) of a light-transmitting inorganic filler is coated with a desired dry coating film thickness. contrast ratio of at t ₀ μm is Is one less than .94, contrast ratio in dry film thickness t _0/2 [mu] m is 0.70
0.90 (t ₀ is 100 to 300), and a dry coating film of a desired thickness t ₀ μm applied to the outer plate surface of the anticorrosive coating composition and the outer plate surface When the color difference (ΔE) is 100, the color difference (ΔE) between the coating film in the wet state of the coated portion and the outer plate surface is observed, and the color difference (ΔE) is 90.
As described above, a step of coating the composition by controlling the amount of the coating composition applied; and (B) a step of coating the undercoated anticorrosion coating composition formed on the outer plate surface in the step (A). And a step of applying a non-organic tin-based hydrolyzable antifouling paint. (A) 'An undercoating anti-corrosion paint (primer) is applied on the entire surface of the outer plate including the bottom, water line, and outer hull of the ship, (i) bisphenol type having an epoxy equivalent of 150 to 1,000. An epoxy resin, (ii) a curing agent for an epoxy resin comprising a polyamidoamine, a polyamine or a modified product thereof, (iii) a coloring pigment of 0.3 to 5% by weight (solid content), and (iv) a light-transmitting inorganic filler. An anticorrosion coating composition containing 25 to 50% by volume (filler volume concentration), (v) a polyol and / or polythiol, (vi) a polyisocyanate-based curing agent, (iii) a coloring pigment 0.3 to 5 % By weight (solid content), and (iv) 25 to 50% by volume (filler volume concentration) of a light-transmitting inorganic filler, at a desired dry film thickness t ₀ μm. Concealment ratio is 0.94 or less Less than 1, contrast ratio of a dry film thickness of t _0/2 [mu] m is 0.70
0.90 (t ₀ is 100 to 300), and a dry coating film of a desired thickness t ₀ μm applied to the outer plate surface of the anticorrosive coating composition and the outer plate surface When the color difference (ΔE) is 100, the color difference (ΔE) between the coating film in the wet state of the coated portion and the outer plate surface is observed, and the color difference (ΔE) is 90.
As described above, the step of applying the coating composition by controlling the amount of the coating composition applied thereto; and (B) the bottom outer panel (A) or the bottom of the outer panel in the '(A)' step. And a step of further applying a non-organic tin-based hydrolyzable antifouling paint on the undercoat anticorrosive paint composition formed on the surface of the outer panel (b) of the water line part. How to paint the outer panel. (A) 'An undercoating anticorrosive paint (primer) is applied on the entire surface of the outer plate including the bottom, the water line, and the outer hull of the ship as a primer (i) bisphenol type having an epoxy equivalent of 150 to 1,000. An epoxy resin, (ii) a curing agent for an epoxy resin comprising a polyamidoamine, a polyamine or a modified product thereof, (iii) a coloring pigment of 0.3 to 5% by weight (solid content), and (iv) a light-transmitting inorganic filler. An anticorrosion coating composition containing 25 to 50% by volume (filler volume concentration), (v) a polyol and / or polythiol, (vi) a polyisocyanate-based curing agent, (iii) a coloring pigment 0.3 to 5 % By weight (solid content), and (iv) 25 to 50% by volume (filler volume concentration) of a light-transmitting inorganic filler, at a desired dry film thickness t ₀ μm. Concealment ratio is 0.94 or less Less than 1, contrast ratio of a dry film thickness of t _0/2 [mu] m is 0.70
0.90 (t ₀ is 100 to 300), and a dry coating film of a desired thickness t ₀ μm applied to the outer plate surface of the anticorrosive coating composition and the outer plate surface When the color difference (ΔE) is 100, the color difference (ΔE) between the coating film in the wet state of the coated portion and the outer plate surface is observed, and the color difference (ΔE) is 90.
As described above, the step of coating by controlling the amount of the coating composition to be applied, (B) the bottom part outer plate (a) of the outer plates in the '(A)' step, or the bottom part A step of further applying a non-organic tin-based hydrolyzable antifouling paint on the coating film of the undercoat anticorrosive paint composition formed on the surface of the outer panel (b) of the water line part; and (C) the above (A) 'On the coating film of the undercoat anticorrosion coating composition formed on the surface of the outer shell of the outer shell in the step,
A method for coating an outer shell of a ship, further comprising a step of applying a top coat for outer hulls. 4. The ship outer panel according to claim 1, wherein the anticorrosion coating composition further contains a thermoplastic resin and / or an ester plasticizer in an amount of 5 to 90% by weight. Painting method. 5. The thermoplastic resin is any one or more of an acrylic resin, a vinyl chloride-isobutyl vinyl ether copolymer, a coumarone indene resin, a xylene resin, and an ester group-containing pentadiene copolymer. The method for coating a ship outer panel according to claim 4, wherein: 6. The outboard marine vessel according to claim 1, wherein said light-transmitting inorganic filler is a powder or a granular material of talc, mica, silica, potassium feldspar or barium sulfate. How to paint the board. 7. The method according to claim 7, wherein the overcoat for the outboard portion is a urethane type.
The method according to claim 3, wherein the paint is an epoxy-based, acrylic-based, or chlorinated polyolefin-based paint. 8. Obtained by the coating method according to claim 1,
A primer layer formed on the surface of the bottom plate of the ship (a) or the bottom plate and the water line (b); and a non-organic tin-based hydrolyzable antifouling formed on the primer layer. A coating vessel having a paint layer. 9. Obtained by the coating method according to claim 2,
A primer layer formed on the entire surface of the outer plate including the bottom portion, the water line portion, and the outer hull portion of the ship, and a bottom portion outer plate (a) of the primer layer, or a portion outside the bottom portion and the water line portion. A coated ship comprising: a nonorganic tin-based hydrolyzable antifouling paint layer formed on a primer layer of a plate (b). 10. A primer layer obtained by the coating method according to claim 3 and formed on the entire surface of an outer plate including a bottom part, a water line part, and a port part of a ship; Non-organic tin-based hydrolyzable antifouling paint layer formed on the bottom layer outer shell (a) or the bottom layer and water line outer layer (b) primer layer, and outer layer outer layer primer layer A coated marine vessel, comprising: a top coat layer formed on an outer periphery formed thereon. 11. The primer layer may further contain a thermoplastic resin and / or an ester plasticizer in an amount of 5 to 90% by weight.
The coated marine vessel according to any one of claims 8 to 10, wherein the coated marine vessel comprises: 12. The method according to claim 12, wherein the thermoplastic resin is an acrylic resin,
The coating vessel according to claim 11, wherein the coating vessel is any one or more of a vinyl chloride-isobutyl vinyl ether copolymer, a coumarone indene resin, a xylene resin, and an ester group-containing pentadiene copolymer. . 13. The coated ship according to claim 8, wherein said primer layer is a powder or a granular material of talc, mica, silica, potassium feldspar or barium sulfate. 14. The coated marine vessel according to claim 10, wherein said outer layer top coat layer is made of a urethane-based, epoxy-based, acrylic-based or chlorinated polyolefin-based paint.