JPH08277372A - Coating composition - Google Patents

Abstract

PURPOSE: To obtain a coating composition comprising a specific non-metallic hydrolyzable resin and an inhibitor for preventing attachment of specific marine organisms, excellent in safety to environment, having excellent inhibiting effect on adhesion of marine organisms over a long period and excellent in physical properties of coating film. CONSTITUTION: This coating composition consists essentially of a copolymer of a monomer mixture of (A) a monomer A of formula I [R<1> to R<3> are each a 1-20C hydrocarbon; X is (meth)acryloxy, maleinoyloxy, etc.] with (B) a monomer B of formula II [R<4> is an alkyl or an aryl; Y is (meth)acryloyloxy, maleinoyloxy, etc.; (n) is an integer of 1-25] and (C) triphenylboronpyridine of formula III. The component C is preferably used in an amount of 0.01-40wt.%, preferably 0.1-30wt.% based on solid content of the coating material. The component A includes e.g. trimethylsilyl (meth)acrylate or trimethylsilylmethyl maleate and the component B includes e.g. methoxyethyl (meth)acrylate or buthoxyethyl itaconate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for preventing the adhesion of marine organisms, and more particularly to a coating composition having excellent environmental safety.

[0002]

2. Description of the Related Art Conventionally, marine organisms such as barnacles, mussels, bryozoans, squirts and seaweed have been attached to submerged parts such as ships and offshore structures, buoys, stationary and aquaculture nets, various water pipes, and pollution control membranes. In order to prevent, a coating composition composed of an organotin hydrolyzable resin and a metal-containing compound mainly containing a compound containing copper such as cuprous oxide or cuprous thiocyanate as a marine organism adhesion inhibitor is widely used. Has been used.

However, the use of organotin compounds is regulated due to the problem of environmental pollution. In particular, small vessels are strictly regulated worldwide because they sail in the inland ocean, and for vessels of 25 m or less, the United States, United Kingdom, France, Australia,
Its use is prohibited in many countries such as EC countries. Even in Japan, the Ministry of Transport has issued usage control notices for domestic vessels, mainly small vessels, but for vessels constructed of aluminum, it is a typical example of small vessels. However, there are exceptionally no regulations. As described above, although the organic tin compound is strictly regulated worldwide due to its environmental impact, the regulation is excluded from the aluminum ships in the following points.

Since aluminum has a high ionization tendency,
When a metal-containing compound is used as a marine organism attachment inhibitor, aluminum may pit due to metal ions produced by the inhibitor, and even a hole may be opened in the hull. Until now, only organotin compounds have been able to prevent the attachment of marine organisms without pitting aluminum. For this reason, organotin compounds are not regulated for aluminum boats.

Considering the influence of the organic tin compound on the environment, a coating composition containing no organic tin compound should be used. For an aluminum ship, especially considering its pitting corrosion, a non-tin compound is used. Development of a coating composition comprising a non-metal hydrolyzable resin and a metal-free marine organism adhesion inhibitor is desired. However, since it is very difficult to develop a coating composition for inhibiting the attachment of marine organisms that does not contain both of the above, it is the current situation that we have no choice but to rely on organotin compounds.

In view of environmental safety, it is not preferable to use a metal-containing marine organism adhesion inhibitor which is widely used at present. This is because, in general, metal-containing compounds are not only toxic to living organisms, but they always remain in the marine environment without decomposition in the form of metals. for that reason,
If a metal compound is continuously used as a marine organism attachment inhibitor, it will remain and increase in the marine environment, but will not decrease. Metal compounds have caused many pollution problems so far. At present, it is feared that if a paint composed mainly of an organotin compound and a metal-containing marine organism adhesion inhibitor is continuously used, it may adversely affect the human body through marine life.

Copper compounds, which are typical compounds of marine organism adhesion inhibitors, are not currently regulated in Japan,
The copper contained in the compound is a concentration factor for marine organisms (concentration factor = concentration of copper in aqueous organisms / concentration of copper in environmental water)
But 4,000 for shellfish and 5,000 for molluscs
0, 1,700 for invertebrates, 1.00 for seaweed
0, 30,000 for phytoplankton, and 6,000 for zooplankton, which are extremely high and have a negative impact on the environment, so regulations have recently been implemented in some countries in Europe. It's starting.

As described above, a coating composition comprising a nonmetallic hydrolyzable resin and a nonmetallic marine organism adhesion inhibitor is strongly desired from the viewpoint of environmental safety, but such a coating composition is desired. Is very difficult to develop, and aluminum vessels have been taken measures to prevent their use even with organotin compounds.

Japan is the first in the world to regulate organotin and establish a position as an advanced country for environmental conservation. From this point as well, there is a strong demand for early development of a coating composition for inhibiting the adhesion of marine organisms which does not contain not only an organotin compound but also a metal-containing compound as an inhibitor for attaching marine organisms.

The performance required for a coating composition that exerts a marine organism adhesion inhibiting effect over a long period of time is that the physiologically active substance used as an inhibitor has a high adhesion inhibiting effect on many types of marine organisms. That is, the resin hydrolyzes in seawater to gradually dissolve the coating film from the surface.
When using a mere slightly water-soluble resin without hydrolysis,
Seawater penetrates too much into the coating film, and only extraction of physiologically active substances precedes it. The above hydrolysis mechanism is necessary in order to dissolve only the resin on the surface of the coating film in seawater and control the permeation of seawater into the coating film.

However, the performance of the coating film is not simply determined by the respective performances of the physiologically active substance and the hydrolyzable resin. The affinity of the entire coating film for seawater, which consists of the affinity of the physiologically active substance for seawater and the affinity of the hydrolyzable resin for seawater, keeps the physiologically active substance at an effective rate to exert the marine organism attachment inhibition performance. Thus, this is only possible if it is exactly suitable for depleting the coating.

When a metal-free organic compound is used as a marine organism adhesion inhibitor, even if it is used in a small amount together with an inorganic marine organism adhesion inhibitor such as cuprous oxide, it is hydrolyzable. It has a great influence on the physical properties of the resin and the performance of inhibiting the adhesion of marine organisms. Therefore, when the total amount of the marine organism adhesion inhibitor is an organic compound containing no metal, the affinity of the entire coating film for seawater as a composite material consisting of a hydrolyzable resin and the marine organism adhesion inhibitor is However, it is very difficult to design a constant and good consumption rate, which does not cause coating film defects and is suitable for continuously releasing the marine organism adhesion inhibitor into seawater at an effective rate.

The affinity of the metal-free marine organism adhesion inhibitor is closely related to the performance of the entire coating film, but the molecular structure of this metal-free marine organism adhesion inhibitor is determined by the affinity for seawater. I can't help it. Since it is used as a marine organism attachment inhibitor, it must have a molecular structure with an excellent attachment inhibiting effect.

Therefore, when the metal-free compound has a molecular structure having a high adhesion-inhibiting effect on marine adherent organisms and is compounded with a non-metal hydrolyzable resin, its coating film For the whole, without causing defects in the coating film,
This composite material can be developed for the first time because it has the affinity to consume the coating film at the rate at which the adhesion inhibitory property of the marine organism adhesion inhibitor is most effectively exhibited.

In the development so far focusing on either the hydrolyzable resin or the marine organism adhesion inhibitor, the organotin hydrolyzable resin and the metal-containing marine organism adhesion inhibitor are not used together, It has not been possible to develop a coating composition capable of inhibiting the adhesion of marine organisms. Many proposals have been made centering on either a metal-free marine organism adhesion inhibitor or a hydrolyzable resin. For example, a coating composition using a boron-based compound as a marine organism adhesion inhibitor other than a copper compound is described in JP-B-54-1571. Since the stain resistance cannot be sufficiently exhibited, it cannot be a coating composition for inhibiting adhesion of marine organisms that does not contain metal.

Hydrolyzable resins are most preferable as the resin capable of releasing the marine organism adhesion inhibitor into seawater for a long period of time and maintaining the biological fouling preventing effect for a long period of time. The hydrolyzable resin has a mechanism in which the hydrolyzable groups are gradually hydrolyzed in seawater and the resin elutes, so that the marine organism attachment inhibitor is always exposed on the surface of the coating film, and the organism attachment inhibition period is maintained for a long period of time. Because you can. Many coating compositions comprising such hydrolyzable resins have also been proposed. For example, various publications such as JP-A-60-500452 and JP-A-63-215780 can be cited.

However, in Japanese Patent Publication No. 60-500452, "As antifouling poison, tributyltin fluoride,
Examples thereof include triphenyl tin hydroxy, triphenyl tin fluoride, tributyl tin oxide, triphenyl tin chloride, Cu ₂ O, ZnO, dithiocarbamate derivatives and cuprous thiocyanate. "
JP-A-3-215780 describes that "by mixing an antifouling agent such as cuprous oxide", and all of them use a metal-containing marine organism adhesion inhibitor.

It is obvious that the metal-containing marine organism adhesion inhibitor, when released into seawater, has an adverse effect on the environment, but as described above, only metal-containing hydrolyzable resins such as organotin compounds are used. In addition, a coating composition that can inhibit the adhesion of marine organisms over a long period of time has not been obtained without using a metal-containing marine organism adhesion inhibitor. In fact, a non-metallic hydrolyzable resin and a non-metallic marine organism adhesion inhibitor are extremely high environmental safety paint products that are not particularly susceptible to pitting corrosion on aluminum vessels. It has not been put to practical use at all.

[0019]

In view of the above circumstances, the present invention does not include not only a metal-containing hydrolyzable resin that adversely affects the environment but also a metal-containing marine organism adhesion inhibitor, and seawater. To provide a coating composition having excellent environmental safety, which does not cause defects such as peeling over time after immersion, is consumed at a constant rate, and exerts a good marine organism attachment-inhibiting effect over a long period of time. It is an object.

[0020]

[Means for Solving the Problems] As described above, when developing a coating composition for inhibiting the adhesion of non-metallic marine organisms, the composition comprises a hydrolyzable resin and a non-metallic marine organism adhesion inhibitor. The coatings must be treated as one composite material in their entirety.

When the physiologically active substance which is the anti-adhesion agent for marine organisms is a non-metallic compound, it can be said that the coating film comprising the hydrolyzable resin and the physiologically active substance is an interactive slightly water-soluble composite material. The hydrolyzable resin causes hydrolysis in seawater, and the mechanism is that the resin after hydrolysis slightly dissolves in seawater, and the physiologically active substance that is a marine organism adhesion inhibitor also slightly dissolves in seawater. It has the property of becoming active for the first time and exerting its medicinal effect on marine periphyton. Therefore, since both of them exert their effect upon contact with water molecules, the affinity of each substance for water molecules is an important factor. Each substance has its own affinity for water,
The coating film made of these substances exerts its function as the slightly water-soluble composite material as a whole.

From the experiments conducted by the present inventors to date,
When the physiologically active substance is an organic compound, the physiologically active substance not only acts as described above but also acts as a positive or negative catalyst for the hydrolysis of the resin. It has been found that the physiologically active substance significantly affects the performance of the slightly water-soluble composite material as a whole. Therefore, when the physiologically active substance is an organic compound, the coating film composed of the hydrolyzable resin and the compound affect each other, and a composite material that exerts its function by dissolving in a small amount in seawater, That is, it can be said that it is an interaction type slightly water-soluble composite material.

The coating composition for inhibiting the adhesion of marine organisms is intended to consume the surface of the coating film with time, that is, to slightly deteriorate it, whereas many other types of coating compositions (for example, , Automotive coating composition) is intended to prevent deterioration of the coating film.Therefore, the former coating composition has a phenomenon not seen in the latter coating composition, that is, the entire coating film. A phenomenon appears in which the performance of the marine organism adhesion inhibitor and the resin are deeply related to each other while interacting with each other.

The development of a novel coating composition excellent in the effect of inhibiting the adhesion of marine organisms, which does not contain any organic tin-based hydrolyzable resin and metal-containing agent for inhibiting the adhesion of marine organisms, which have been conventionally used, is based on the above-mentioned mutual development. This is achieved by uniformly consuming the action-type slightly water-soluble composite material at a very minute rate of several microns per month. This does not hold only by controlling the hydrophilicity of the physiologically active substance or by controlling the hydrophilicity of the hydrolyzable resin, and high performance can only be achieved by controlling the balance of hydrophilicity of both and other interactions. It is possible to develop interactive water-soluble composite materials.

The present inventors have focused their attention on organic silyl resins as a novel hydrolyzable resin which replaces the organic tin resins. As a result, the introduction of only the organic silyl group conventionally proposed for this type of resin into the resin does not show sufficient film depletion property, and the alkoxy or aryloxyethylene with the organic silyl group is not recognized in the resin. It was found that when an oxide group was introduced, a resin having a good coating film depletion property was obtained, and this was already proposed as Japanese Patent Application No. 5-269695.

Here, if it is possible to develop a coating composition using only an organic silyl resin and a non-metal compound as a marine organism adhesion inhibitor, a metal-containing hydrolyzable resin that adversely affects the environment. It is extremely environmentally safe and does not contain metal-containing marine organism attachment inhibitors and does not cause pitting corrosion, so it will be possible to develop excellent coating compositions especially for aluminum ships. Considering this, we have started to develop a coating composition which does not contain not only this organotin compound but also the metal-containing marine organism adhesion inhibitor.

In developing such a coating composition,
A coating composition consisting of a non-metal hydrolyzable resin and a non-metal marine organism adhesion inhibitor generally shows not only adhesion of marine organisms in a very short time but also coating film defects such as peeling. Therefore, it takes a lot of labor and time for the above development.

However, as a result of earnest studies by the present inventors, as a nonmetallic hydrolyzable resin, a resin in which an alkoxy or aryloxyethylene oxide group was introduced into the molecule together with an organic silyl group was used, while a nonmetallic metal was used. The coating composition using triphenylboron viridine as a system-based marine organism adhesion inhibitor does not contain any metal-containing resin and metal-containing marine organism adhesion inhibitor, and is very environmentally safe. The coating film has a high hardness during film formation, does not cause peeling and other coating results after immersion in seawater, and in addition, triphenylboron viridine is slowly released into seawater at a rate effective for inhibiting the adhesion of marine organisms. A hydrolyzable self-polishing coating composition that can consume the film at a constant rate and exerts an excellent marine organism adhesion inhibiting effect for a long time It found that, ItaruTsuta to the completion of the present invention.

That is, the present invention provides the following general formula (1); (In the formula, each of R ^{1 to} R ³ is a hydrocarbon group having 1 to 20 carbon atoms and may be the same group or different groups. X is an acryloyloxy group or a methacryloyloxy group. , A maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group) and the following general formula (2): Y- (CH ₂ CH ₂ O) nR ⁴ ... ( 2) (In the formula, R ⁴ is an alkyl group or an aryl group. Y
Is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group. n is an integer of 1 to 25. )
And a copolymer of a monomer mixture containing a monomer B represented by the following structural formula (3);

[0030]

Embedded image

A resin component and a marine organism adhesion inhibitor are composed only of a metal-free polymer and a metal-free organic inhibitor, containing triphenylboron pyridine represented by It relates to a coating composition.

[0032]

In the coating composition of the present invention,
As one of the essential components, one or more kinds of the monomer A represented by the general formula (1) and one kind of the monomer B represented by the general formula (2) or 1 of other monomers containing 2 or more kinds and copolymerizable with them, if necessary.
A copolymer of a monomer mixture containing one kind or two or more kinds (hereinafter, referred to as a copolymer AB) is used.

As represented by the general formula (1), the monomer A has an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly a monoalkyl ( C1-6) ester maleinoyloxy group], fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group], or itaconoyloxy group [mainly monoalkyl (C1-6) ) Ester itaconoyloxy group] and a triorganosilyl group.

In the triorganosilyl group, the three hydrocarbon groups (R ^{1 to} R ³ ) may be the same group or different groups. Specifically, a linear or branched alkyl group or substituted alkyl group having 20 or less carbon atoms such as methyl, ethyl, propyl, and butyl; cyclopropyl,
Cyclic alkyl groups such as cyclohexyl; aryl groups such as phenyl groups and polycyclic aryl groups such as naphthyl groups. Further, as the substituent of the substituted alkyl group,
Halogen, aryl group, acyl group, alkoxy group, aryloxy group, nitro group, amino group, etc. are substituted aryl groups.
Examples of the substituent of the group include a halogen, an alkyl group, an acyl group, an alkoxy group, an aryloxy group, a nitro group, an amino group and the like.

Examples of the monomer A having a (meth) acryloyloxy group in the molecule include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate and tri-n-propylsilyl ( (Meth) acrylate, tri-i-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate
, Tri-i-butylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-i-amylsilyl (meth) acrylate, tri-n-hexyl Silyl (meth) acrylate, tri-n-octyl silyl (meth) acrylate, tri-n-dodecyl silyl (meth) acrylate, tri-n-icosane silyl (meth) acrylate,
Examples include triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, tri-2-methoxyethylsilyl (meth) acrylate, and the like. .

Other examples having a (meth) acryloyloxy group in the molecule include ethyldimethylsilyl (meth) acrylate, dimethyl n-propylsilyl (meth) acrylate, dimethyl i-propylsilyl (meth). ) Acrylate, n-butyldimethylsilyl (meth)
Acrylate, s-butyldimethylsilyl (meth) acrylate, i-butyldimethylsilyl (meth) acrylate, t-butyldimethylsilyl (meth) acrylate
N-amyldimethylsilyl (meth) acrylate,
i-Amyldimethylsilyl (meth) acrylate, n-
Icosan dimethylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, di i
-Propyl stearyl silyl (meth) acrylate, dicyclohexyl phenyl silyl (meth) acrylate,
Lauryldiphenylsilyl (meth) acrylate, ethyldi-n-octylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, cyclohexyldi-p-tolylsilyl (meth) acrylate, di t-Butylmethylsilyl (meth) acrylate, n-icosandi o-nitrophenylsilyl (meth) acrylate
I-amyldi m-chlorophenylsilyl (meth) acrylate, ethylmethyl n-propylsilyl (meth)
Examples thereof include acrylate, i-amyl t-butylmethylsilyl (meth) acrylate, o-cyanophenylcyclohexylnaphthylsilyl (meth) acrylate and the like.

As those having a maleinoyloxy group in the molecule, trimethylsilyl methyl maleate, triethyl silyl n-propyl maleate, tri i-propyl silyl methyl maleate, tri i-propyl silyl n-amyl maleate, Tri-n-propylsilyl n-amyl male
Tri-propylsilyl i-amyl maleate, tri-n-butylsilyl n-butyl maleate, t-butyldiphenylsilyl methyl maleate, t-butyldiphenylsilyl n-butyl maleate, tri-n-butylsilyl 2-ethylhexyl maleate, tris-butylsilyl n-octyl maleate, tri n-amylsilyl phenyl maleate
Tri-amylsilylbenzyl maleate, tri-n-
Dodecylsilyl o-nitrophenyl maleate, tri-n-
Icosane silyl p-tolylmaleate, triphenylsilyl 2-methoxyethyl maleate, tribenzylsilyl m
-Bromophenyl maleate, tri-2-methoxyethylsilyl cyclohexyl maleate, ethyldimethylsilylmethyl maleate, dimethyl n-propylsilylmethyl maleate, dimethyl i-propylsilyl n-amyl maleate
N-butyldimethylsilyl i-amyl maleate, s
-Butyldimethylsilylphenyl maleate, i-butyldimethylsilyl cyclohexyl maleate, t-butyldimethylsilyl o-N, N-dimethylaminophenyl maleate, n-amyldimethylsilyl t-butyl maleate,
i-Amyldimethylsilyl 2-methoxyethyl male
, N-icosane dimethylsilyl 2-ethoxyethyl maleate, ethyl di-n-octyl silyl p-tolylmaleate, t-butyldiphenylsilyl 3-methoxycyclohexyl maleate, di-t-butylmethylsilyl i- Propyl maleate, n-icosandi o-nitrophenylsilyl m-fluorophenyl maleate, i-amyldi m-chlorophenylsilyl 2-ethylhexyl maleate, ethylmethyl n-propylsilyl i-butyl maleate, i −
Amyl t-butylmethylsilyl s-butyl maleate, o
-Cyanophenyl cyclohexyl naphthyl silyl methyl maleate and the like.

As those having a fumaroyloxy group in the molecule, trimethylsilylmethyl fumarate, triethylsilyl n-propyl fumarate, tri n-propylsilyl n-amyl fumarate, tri i-propylsilyl i
-Amyl fumarate, tri-n-butylsilyl 2-ethylhexyl fumarate, tri-s-butylsilyl n-octyl fumarate, tri-n-amylsilylphenyl fumarate
I-amylsilylbenzyl fumarate, tri-n
-Dodecylsilyl o-nitrophenyl fumarate, tri-n-icosanesilyl p-tolyl fumarate, triphenylsilyl 2-methoxyethyl fumarate, tribenzylsilyl m-bromophenyl fumarate, tri-2 -Methoxyethylsilyl cyclohexyl fumarate, ethyldimethylsilylmethyl fumarate, dimethyl n-propylsilylmethyl fumarate, dimethyl i-propylsilyl n
-Amyl fumarate, n-butyldimethylsilyl i-amyl fumarate, s-butyldimethylsilyl phenyl fumarate, i-butyldimethylsilyl cyclohexyl fumarate, t-butyldimethylsilyl o-N, N- Dimethylaminophenyl fumarate, n-amyldimethylsilyl t-butyl fumarate, i-amyldimethylsilyl 2-methoxyethyl fumarate, n-icosane dimethylsilyl 2-ethoxyethyl fumarate, ethyl diethyl n-octylsilyl p-tolyl fumarate, t-butyldiphenylsilyl 3-methoxycyclohexyl fumarate, di-t-butylmethyl i-propyl fumarate, n-icosane di-o-nitrophenylsilyl m-fluorophenyl fumarate Maleate, i-amyldi m-chlorophenylsilyl 2-
Examples thereof include ethylhexyl fumarate, ethylmethyl n-propylsilyl i-butyl fumarate, i-amyl t-butylmethylsilyl s-butyl fumarate and o-cyanophenylcyclohexylnaphthylsilylmethyl fumarate.

As those having an itaconoyloxy group in the molecule, trimethylsilylmethyl itaconate, triethylsilyl n-propyl itaconate, tri n-propylsilyl n-amyl itaconate, tri i-propyl silyl i-amyl itacone Tri-n-butylsilyl 2-ethylhexyl itaconate, tri-s-butylsilyl n-octyl itaconate, tri n-amyl silyl phenyl itaconate, tri i-amyl silyl benzyl itaconate, tri n-dodecyl silyl o-Nitrophenyl itaconate, tri-n-icosane silyl p-triluitaconate, triphenyl silyl 2-methoxyethyl itaconate, tribenzyl silyl m-bromophenyl itaconate, tri-2-methoxyethyl silyl cyclohexyl itaconate -To Ethyldimethylsilyl methyl itaconate Ne - DOO, dimethyl n- propylsilyl methyl itaconate Ne -
G, dimethyl i-propylsilyl n-amylitacone
N-butyldimethylsilyl i-amylitacone
, S-butyldimethylsilylphenyl itanetate,
i-Butyldimethylsilylcyclohexyl itacone
T-butyldimethylsilyl o-N, N-dimethylaminophenyl itaconate, n-amyldimethylsilyl t-butyl itaconate, i-amyldimethylsilyl 2
-Methoxyethyl itaconate, n-icosane dimethylsilyl 2-ethoxyethyl itaconate, ethyl di-n-
Octylsilyl p-tolulytaconate, t-butyldiphenylsilyl 3-methoxycyclohexylitacone
Di-t-butylmethyl i-propyl itaconate, n
-Icosandi o-nitrophenyl silyl m-fluorophenyl itaconate, i-amyldi m-chlorophenyl silyl 2-ethylhexyl itaconate, ethylmethyl n-propylsilyl i-butyl itaconate, i-amyl t- Butylmethylsilyl s-butylitaconate, o
-Cyanophenylcyclohexylnaphthylsilylmethyl itaconate and the like.

The monomer B is, as represented by the general formula (2), an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group [mainly monoalkyl (Y) as an unsaturated group (Y) in the molecule. C1-6) ester maleinoyloxy group], fumaroyloxy group [mainly monoalkyl (C1-6) ester fumaroyloxy group,
Alternatively, it has an itaconoyloxy group (mainly a monoalkyl (carbon number 1 to 6) ester itakonoyloxy group) and also has an alkoxy or aryloxyethylene oxide group.

In the alkoxy or aryloxyethylene oxide group, the ethylene oxide group has a degree of polymerization (n) of 1 to 25. Further, as the alkyl group or aryl group (R ⁴ ), methyl, ethyl, propyl,
Examples thereof include linear or branched alkyl groups having 12 or less carbon atoms such as butyl; cyclic alkyl groups such as cyclohexyl and substituted cyclohexyl; aryl groups and substituted aryl groups. Substituted aryl groups include halogen and 1 carbon atoms.
There are up to about 8 alkyl groups, acyl groups, aryl groups substituted with nitro groups, amino groups and the like. In addition,
When two or more monomers B are used, the average value of the degree of polymerization (n) of ethylene oxide groups in the whole monomer B may not be an integer. There is no problem even if a mixture of two or more of the above is used.

Examples of the monomer B having a (meth) acryloyloxy group in the molecule include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and propoxyethyl (meth). Acrylate, butoxyethyl (meth) acrylate, hexaoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethyleneglycol (Meth) acrylate, ethoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and the like.

Further, those having a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group in the molecule include, for example, methoxyethyl n-butyl maleate, ethoxydiethylene glycol methyl maleate,
Ethoxytriethylene glycol methyl maleate, propoxydiethylene glycol methyl maleate, butoxyethyl methyl maleate, hexaoxyethyl methyl maleate, methoxyethyl n-butyl fumarate, ethoxydiethylene glycol methyl fumarate, ethoxytriethylene glycol Examples thereof include trimethylmethyl fumarate, propoxydiethylene glycol methyl itaconate, butoxyethyl methyl itaconate, and hexaoxypolyethylene glycol methyl itaconate.

Other monomers copolymerizable with these monomers A and B include, for example, acrylic acid ester, methacrylic acid ester, styrene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and the like. Various vinyl-based monomers such as vinyl esters, vinyltoluene, α-methylstyrene, crotonic acid esters, and itaconic acid esters can be used.

In the monomer mixture, the proportions of the monomers A and B and the other monomers copolymerizable with them can be appropriately set according to the purpose of use of the coating composition, but in general, they are single monomers. It is preferable that the amount of the monomer A is 1 to 95% by weight, the amount of the monomer B is 1 to 95% by weight, and the amount of other monomer copolymerizable with them is 0 to 98% by weight.

The copolymer AB is obtained by polymerizing such a monomer mixture in the presence of a vinyl polymerization initiator by various known methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization. Can be obtained. When this copolymer AB is used for paints, it is convenient to dilute it with an organic solvent to obtain a polymer solution having an appropriate viscosity. For that purpose, it is desirable to adopt a solution polymerization method or a bulk polymerization method. .

As the above-mentioned vinyl polymerization initiator, an initiator used in ordinary polymerization can be selected and used according to the polymerization method. Specific examples include 2,2'-azobis-isobutyronitrile and 2,2'-azobis-2-
Methyl butyronitrile, 2,2'-azobis-2,4-
Dimethylvaleronitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis Azobis initiators such as-(2-amidinopropane) dihydrochloride, benzoylperoxide, t-butylperoxy (2-ethylhexanoate), t-butylperoxyisopropylcarbonate, t- Examples thereof include peroxide type initiators such as butyl peroxybenzoate.

The organic solvent may be selected from various organic solvents according to the kind of the monomer and the polymerization temperature, and one kind or a mixture of two or more kinds may be used. Specifically, pentane, hexane, heptane and other aliphatic hydrocarbon solvents, benzene, toluene, xylene and other aromatic hydrocarbon solvents, ethyl acetate, butyl acetate, ester solvents such as isobutyl acetate, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone and cyclohexanone, ethanol, isopropanol,
Examples include alcohol solvents such as butanol.

The weight average molecular weight of the copolymer AB obtained by such a method is preferably in the range of 1,000 to 300,000. If the molecular weight is too low, it will be difficult to form a normal coating film, and if it is too high, a large amount of thinner will be required at the time of coating, resulting in the problem that a large number of coatings will be required to obtain the required thickness. . The viscosity of the polymer solution containing this copolymer AB is 1 at 25 ° C.
It is conveniently 50 poise or less, for which the solids content of the polymer solution should be in the range 5 to 90% by weight, preferably 15 to 85% by weight.

In the present invention, it is essential to use the copolymer AB obtained by the above method as the resin component. However, a small amount of a polymer other than those mentioned above may be used in combination unless the effects of the present invention are impaired. May be. From the environmental safety viewpoint, the other polymer needs to be a polymer containing no metal.
“Metal-free” means that one of the constituent elements of the polymer does not contain metal elements such as copper, tin, and mercury, which have a problem in environmental safety, and impurities derived from the synthetic raw materials of the polymer. It does not mean that even a trace amount of the above metal is not included.

The coating composition of the present invention uses triphenylboron viridine as another essential component.
The amount of this triphenylboron viridine used is usually 0.01 to 40% by weight, preferably 0.1 to 40% by weight in the coating solid content.
A range of 30% by weight is preferable. If the amount is too small, the effect of inhibiting adhesion of marine organisms cannot be expected, and if the amount is too large, defects such as cracks and peeling are likely to occur in the coating film, and a good inhibitory effect cannot be obtained.

In the present invention, in addition to the above triphenylboron viridine, other marine organism adhesion inhibitors known in the paint industry may be used in combination, if necessary. In view of environmental safety, it is necessary that the other marine organism adhesion inhibitors be organic inhibitors that do not contain metals. "Metal-free"
Means that one of the constituent elements of the organic inhibitor (organic compound) does not contain metal elements such as copper, tin, and mercury, which have a problem in environmental safety, and is derived from the synthetic raw material of the organic inhibitor. It does not mean that even a trace amount of the above metal as an impurity is not included.

Examples of such metal-free organic inhibitors include N-trihalomethylthiophthalimide, N-arylmaleimide, 3-substituted amino-1,3-thiazolidine-2,4-dione, dithiocyano compounds, There are various organic compounds that do not have a metal as a constituent element, such as triazine-based compounds.

Specifically, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-N ′ -Dichlorophenylurea,
4,5-Dichloro-N-octyl-isothiazoline-3
-One, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N'-phenyl-N'-fluorodichloromethylthiosulfamide, tetramethylthiuram disulfide, 2,4,6-trichlorophenylmaleimide , 2,3,5,6-Tetrachloro-4-methylsulfonyl-pyridine, diodomethylparatolylsulfone, 2- (4-thiazolyl) benzimidazo-
And 2- (thiocyanomethylthio) benzothiazole.

In the present invention, the amount of such other marine organism attachment inhibitor used is such that the total amount with triphenylboronpyridine is usually 50% by weight or less, preferably 40% by weight, in the coating solid content. The following range is good. If too much is used, the coating film properties will deteriorate and it will be difficult to obtain a good biofouling inhibiting effect.

To the coating composition of the present invention, an oil component such as rosin or a derivative thereof, silicone oil, and liquid paraffin may be added, if necessary, for the purpose of adjusting the dissolution rate. Specific examples thereof include rosin, hydrogenated rosin, maleated rosin, dimethyl silicone oil, methylphenyl silicone oil, polyether modified silicone oil, paraffin wax, petrolatum and polybutene.

The coating composition of the present invention includes, in addition, a valve pattern used in ordinary coatings, coloring agents such as pigments and dyes such as titanium dioxide and talc, anti-sagging agents commonly used in coatings, and color separation prevention. Agents, anti-settling agents, antifoaming agents, etc., and plasticizers, other resins, solvents, etc. can be added as necessary. Some pigments and dyes used in ordinary paints contain metal, but their safety to the environment is much lower than that of metal-containing marine organism adhesion inhibitors, so use these. It can also be done. Examples of the plasticizer include chlorinated paraffin, dialkyl phthalate, tricresyl phosphite, triphenyl phosphite and the like.

The coating composition of the present invention can be produced by a conventionally known coating production method, and the coating method can also be spray coating, brush coating, roller coating, dipping or the like. It can be painted using any means.

[0059]

The coating composition of the present invention essentially contains a specific hydrolyzable resin having a triorganosilyl group in its side chain and an alkoxy or aryloxyethylene oxide group, and triphenylboron pyridine. As a component, the resin component and the marine organism adhesion inhibitor are characterized by containing substantially no metal.The coating film, which is a composite material made of it, has an affinity for seawater as a whole and is a depleting property of the coating film. It has been designed to be extremely good for a long time, even though it does not use any metal-containing hydrolyzable resin and metal-containing marine organism adhesion inhibitor, which have environmental safety problems. Excellent adhesion inhibition performance.

Further, the coating composition of the present invention is not only free from coating film defects such as peeling and cracking, but also wears out at a constant and good rate. It does not form a layer and exhibits very good recoatability as compared with the conventional non-hydrolyzable paint. Furthermore, since no metal-containing marine organism adhesion inhibitors are used, there is no risk of pitting corrosion on aluminum, and it is suitable for use on aluminum vessels where the use of organotin compounds is exceptionally permitted. Very suitable.

Further, the coating film surface can always be kept smooth due to good solubility of the coating film. For this reason, the fuel consumption of ships and the like can be reduced, which in turn can contribute to the prevention of global warming due to carbon dioxide. Furthermore, in the coating composition of the present invention, a coating composition for inhibiting the adhesion of marine organisms cannot be colored in a vivid color because cuprous oxide or the like is used. It is a coating composition that can be colored and has excellent designability.

[0062]

EXAMPLES Next, the present invention will be specifically described with reference to production examples, examples and comparative examples. In addition, the part in an example is a weight part and molecular weight is polystyrene conversion weight average molecular weight by GPC. In addition, the monomer A (A ₁
To A ₈ ) are monomers represented by the general formula (1), and R ^{1 to} R ³ and X in the general formula (1) are as shown in Table 1 below. Also, the monomer B used in the production example
(B _{1 to} B ₈ ) are monomers represented by the general formula (2), and Y, n and R ⁴ in the general formula (2) are as shown in Table 2 below.

[0063]

[Table 1]

[0064]

[Table 2]

Production Examples 1 to 5 In a flask equipped with a stirrer, the solvent a was charged in accordance with the formulation shown in Table 3 below, the temperature was raised to a predetermined reaction temperature, and the monomers A and B were stirred. A mixed solution of the other monomer and the polymerization catalyst a was dropped into the flask over 3 hours, and after the dropping was completed, the temperature was maintained at the same temperature for 30 minutes. Then, the mixture of the solvent b and the polymerization catalyst b was added dropwise over 20 minutes, and the mixture was added at the same temperature for 2 minutes.
The polymerization reaction was completed by continuing stirring for an hour. Finally, a diluting solvent was added to dilute the solution to obtain each polymer solution S _{1 to} S ₅ .
In Table 3, "perbutyl I" as a polymerization catalyst [trade name of NOF CORPORATION] is t-butyl peroxyisopropyl carbonate.

[0066]

[Table 3]

Production Example 6 Monomer A, Monomer B, other monomers and a polymerization catalyst were charged in a heat and pressure resistant container in accordance with the formulation shown in Table 4 below, and the mixture was completely sealed and shaken. While raising the temperature to a predetermined reaction temperature, shaking was continued at the same temperature for 8 hours to complete the reaction.
Next, a diluting solvent was added and the mixture was shaken for 1 hour to dissolve it, to obtain a polymer solution S ₆ . In the table, "perbutyl I" as a polymerization catalyst is the same as in Table 3.

Production Examples 7 and 8 Solvent a, monomer A, monomer B, other monomer and polymerization catalyst were charged in a flask equipped with a stirrer according to the formulation shown in Table 4 below, and the mixture was stirred. The temperature was raised to a predetermined reaction temperature, and stirring was continued at the same temperature for 6 hours to complete the reaction. Then, it was diluted with a diluting solvent to obtain polymer solutions S ₇ and S ₈ .

[0069]

[Table 4]

Examples 1 to 20 Using the polymer solutions S _{1 to} S ₈ , the respective components were mixed according to the compounding compositions shown in the following Tables 5 to 9 (numerical values in the tables are% by weight). Mix and disperse with a homomixer at 000 rpm,
Twenty coating compositions were prepared. In each table, "TS
"F-4445" [trade name of Toshiba Silicone Co., Ltd.] is a polyether modified silicone oil, and "Disparlon A630-20X" [trade name of Kusumoto Kasei Co., Ltd.] and "Benton" SD-2 "(trade name of National Red Co., Ltd.) is an additive for preventing sagging.

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

[Table 7]

[0074]

[Table 8]

[0075]

[Table 9]

Comparative Example 1 "LALOFLEX MP-15" (trade name, manufactured by BASF, vinyl chloride resin currently commonly used in coating compositions for inhibiting non-tin based marine organism adhesion) 15 parts, 20 parts of rosin, 14 parts of triphenylboron pyridine, 3 parts of 2-methylthio-4-t-butylamino-6-cyclopropylamino-S-triazine, 2 parts of talc, 2 parts of carbon black, 2 parts of zinc oxide, Disparlon A630-2
0X "[trade name of Kusumoto Kasei Co., Ltd.] 3 parts, xylene 2
A coating composition was prepared by mixing 9 parts and 10 parts of butyl acetate and mixing and dispersing with a homomixer at 2,000 rpm.

Comparative Example 2 5 parts of "Pryolite S-5B" (trade name, manufactured by Gutsdoyer, styrene / butadiene copolymer), 10 parts of rosin
Part, triphenylboron pyridine 20 parts, rouge 15 parts,
Mix 40 parts of xylene and 10 parts of butyl acetate,
A coating composition was prepared by mixing and dispersing with a homomixer at 0 rpm.

Comparative Examples 3 to 5 Polymer solutions S ₃ , S ₄ , S ₆ and S ₇ were used and the following Table 1 was used.
Each component was mixed according to the compounding composition shown in 0 (numerical values in the table are% by weight) and mixed and dispersed by a homomixer of 2,000 rpm to prepare three kinds of coating compositions. In addition, in Table 10,
"TSF-4445", "Days Baron A630-20"
X "and" Benton SD-2 "are shown in Tables 5 to 9 above.
Is the same as in.

[0079]

[Table 10]

The above Examples 1 to 20 and Comparative Examples 1 to 5
With respect to each coating composition, the coating film consumption test, marine organism adhesion inhibition test, adhesion test and crack resistance test were conducted in the following manner.

<Coating Film Depletion Test> Each coating composition was sprayed twice on a surface of a steel plate (100 mm × 100 mm × 1 mm) with anticorrosion coating on both sides so that the dry coating film thickness was 200 μm each time. -Painted and dried in a dryer at a temperature of 20 ° C for 1 week to prepare a test piece. By attaching the above test piece to a cylindrical drum with a diameter of 50 cm, rotating it in seawater for a certain period, and measuring the consumed film thickness of the coating film, 4
It was measured every 24 months for 24 months. Further, the average speed of coating film thickness consumption (μm / month) was calculated. These results are
The chickens shown in Table 11 were used. In addition, if the coating film thickness consumption average speed is 3 μm / month or more, it correlates with good marine organism attachment inhibition performance. Further, when a coating film defect such as peeling occurred during the coating film consumption test, the consumption film thickness could not be measured, and therefore the subsequent film thickness measurement was not performed.

<Aquatic organism adhesion inhibition test> A tar epoxy-based rust preventive paint was applied to a sandblasted steel sheet once per 1 time.
Spray coating was applied twice to obtain a dry film thickness of 25 μm, and further, a tar vinyl series seal coat was applied so that the dry film thickness was 70 μm. Each coating composition was applied twice by spray coating so that the dry film thickness was 100 μm each time, and then dried for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75%. Then, a test piece was prepared. These test pieces were tested at Aioi Bay, Aioi City, Hyogo Prefecture, 1.
A stationary immersion test was conducted at a depth of 5 m. The ratio of the occupied area (adhered area) of adhering organisms on the test piece was measured every 3 months for 24 months. The results are shown in Table 12. Further, after 24 months, the types of organisms attached to the test pieces were examined, and the results are shown in Table 13.

<Adhesion Test> A blast steel sheet was spray-coated twice with a tar-epoxy type anticorrosive coating so that a dry film thickness of 125 μm was obtained, and then a tar vinyl-based sealant was applied. -Coating was performed so that the dry film thickness was 70 μm. On top of this, apply each coating composition to a dry film thickness of 10
After being coated twice by spray coating so as to have a thickness of 0 μm, it was dried for 1 week in a constant temperature and humidity chamber at a temperature of 20 ° C. and a humidity of 75% to prepare a test piece. The test piece was dipped in artificial seawater, pulled up every 3 months, and subjected to a burlap test at 2 mm intervals for 24 months. The adhesiveness was evaluated as ◯ (pass) when the number of peeled pieces by this test was 0/25, and as x (failed) when the number of peeled pieces was 1 or more / 25 pieces. The results are as shown in Table 14.

<Crack resistance test> In the adhesion test, when the test piece was pulled out from the artificial seawater, the coating film was visually observed to check for the occurrence of cracks. Those without cracks were marked with O (pass), and those with cracks were marked (fail). The results are as shown in Table 15.

[0085]

[Table 11]

[0086]

[Table 12]

[0087]

[Table 13]

[0088]

[Table 14]

[0089]

[Table 15]

As is clear from the results of Tables 11 to 15, the coating compositions of Comparative Examples 1 to 5 showed unsatisfactory results in terms of coating film consumption rate, coating film physical properties, and marine organism adhesion inhibiting performance. However, each of the coating compositions of Examples 1 to 20 of the present invention shows satisfactory results in any test. From these results as well, the coating composition of the present invention shows that the coating composition of the present invention is non-metallic. It can be seen that the decomposable resin and the non-metallic marine organism adhesion inhibitor are excellent in environmental safety and have good performance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 171/02 PLQ C09D 171/02 PLQ

Claims (1)

[Claims] 1. The following general formula (1); (In the formula, each of R ^{1 to} R ³ is a hydrocarbon group having 1 to 20 carbon atoms and may be the same group or different groups. X is an acryloyloxy group or a methacryloyloxy group. , A maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group) and the following general formula (2): Y- (CH ₂ CH ₂ O) nR ⁴ ... ( 2) (In the formula, R ⁴ is an alkyl group or an aryl group. Y
Is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group. n is an integer of 1 to 25. )
And a copolymer of a monomer mixture containing the monomer B represented by the following structural formula (3); A coating composition containing triphenylboron pyridine represented by as an essential component, wherein the resin component and the marine organism adhesion inhibitor are composed only of a metal-free polymer and a metal-free organic inhibitor. .