JPH0480205A - Film-forming polymer-metal complex resin - Google Patents

Abstract

PURPOSE:To block the interaction between metal ions and prevent the formation of ion associates by preparing the title resin comprising a specific repeating unit derived from an ethylenically unsatd. monomer and a repeating unit corresponding to another ethylenically unsatd. monomer. CONSTITUTION:An ethylenically unsatd. monomer having an acid group and one having no acid group are radical copolymerized in a soln. to give a copolymer having pendant acid groups, which is reacted with an oxide, a hydroxide, a chloride, a sulfide, or a basic carbonate salt, etc., of a transition metal in an equivalent amt. or higher and simultaneously with a monobasic org. acid in an equivalent amt. or higher to give a polymer metal salt. The salt is reacted with a compd. which functions as a ligand, giving the title resin comprising a copolymer having a number-average mol.wt. of 2,000-100,000 and comprising 5-80wt.% repeating units of the formula (wherein R<1> is H, methyl, or alkoxycarbonyl; R<2> is H or alkoxycarbonyl; A is an acid ion-terminated pendant group; M is a transition metal; L is an org. ligand provided at least one of L is an org. acid ion; 2<=m<=n-1; and n is the coordination number of M) and 95-20wt.% repeating unit corresponding to the ethylenically unsatd. monomer having no acid group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a film-forming polymer metal complex resin useful as a vehicle resin for antifouling paints.

Main plate ■Background Antifouling paints using trialkyltin polymer compounds as vehicles are known. This antifouling paint is unique in that it suppresses the elution amount of the antifouling agent to the minimum level required to maintain antifouling properties, and elutes a constant amount over a long period of time. In this paint, the trialkyltin polymer compound used as a vehicle is hydrolyzed in a slightly alkaline atmosphere of seawater, releasing a tin compound, and the vehicle becomes water-soluble and the paint film is worn out, which smooths out the unevenness of the paint film. , which reduces seawater frictional resistance on ships and contributes to fuel cost savings.

The vehicle resin of this self-polishing paint is, for example, a copolymer of tributyltin (meth)acrylate and a comonomer containing no free carboxyl groups. However, due to concerns about the impact of trialkyltin on the ecosystem,
It is desired to develop a vehicle resin for self-polishing antifouling paints to replace trialkyltin polymer compounds.

The present inventors proposed, in Japanese Patent Application No. 113124/1986, as a resin that satisfies such demands, for example, by adding (meth)acrylic acid to a divalent or higher heavy metal instead of the above tributyltin (meth)acrylate copolymer. We have developed a metal-containing resin having repeating units in the form of salts bound to other monobasic organic acids through ionic bonds. However, in such a polymeric metal salt resin, metal ions associate in the solution and in the coating film to form a pseudo-crosslinked structure, so that the resin has a high viscosity in the solution and a strong cohesive force in the coating film. As a result, it becomes difficult to make a paint using the resin highly solid, which adversely affects the rate of paint film wear and the sustained release of metal ions.

Keiko dish small view! The present invention was first filed by the inventors in Japanese Patent Application No. 1983-1983. 11312
By further bonding a ligand to the metal atom in the polymeric metal salt resin disclosed in No. 4, etc., we succeeded in blocking the interaction between metal ions and suppressing the formation of ionic aggregates.

Therefore, the present invention is based on (a) formula % formula % (wherein R1 is a hydrogen atom, methyl or an alkoxycarbonyl group, R2 is a hydrogen atom or an alkoxycarbonyl group, A is a pendant group whose terminal is an acid ion, and M is a transition The metal element, L is an organic ligand, at least one of which is an organic acid ion, m is an integer expressed by 2≦m≦n-1, and n is the coordination number of the central metal atom M. .)
5 to 80% by weight of repeating units represented by; (b) containing 95 to 20% by weight of repeating units corresponding to other ethylenically unsaturated monomers and having a number average molecular weight of 2,000
The present invention relates to a film-forming polymeric metal complex resin characterized by comprising a copolymer having a molecular weight of 100,000 to 100,000.

By complexing the metal atoms bonded to the polymer pendant acid groups, ionic association is suppressed, resulting in a significantly lower solution viscosity at the same solids concentration than the corresponding polymeric metal salt resin, and further improves coating film formation. Improvements were seen in the depletion rate and sustained release of metal ions. Furthermore, the resin of the present invention is not easily affected by other metal ions in solution, and therefore can coexist with metal compounds such as cuprous oxide and zinc oxide in paint without impairing storage stability.

The resin of the present invention can be produced by various methods, including first producing a copolymer having a corresponding pendant acid group, then converting this into a polymeric metal salt, and finally converting it into a polymeric metal salt. A method of reacting a ligand with is preferred.

A copolymer having pendant acid groups can be produced by radical polymerizing an ethylenically unsaturated monomer having an acid group and an ethylenically unsaturated monomer having no acid group in a solution using a conventional method. I can do it.

Examples of monomers having carboxyl groups as acid groups include acrylic acid, methacrylic acid, and hydroxy group-containing monomers such as maleic acid monoalkyl esters, itaconic acid monoalkyl esters, and 2-hydroxyalkyl (meth)acrylates. and half esters with dibasic carboxylic acids such as phthalic acid, succinic acid, and maleic acid.

As a monomer having a sulfonic acid group as an acid group, p-
Examples include styrene sulfonic acid and 2-methyl-2-acrylamidopropanesulfonic acid.

Examples of monomers having a phosphoric acid group as an acid group include acidophosphoxypropyl methacrylate, 3-chloro-2-acidophosphoxypropyl methacrylate, and acidophosphoxyethyl methacrylate.

Examples of monomers without pendant acid groups include ethylene,
Hydrocarbons such as propylene, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene; methyl (
meth)acrylate, ethyl(meth)acrylate, n
-Butyl (meth)acrylate, 2-ethylhexyl (
Alkyl (meth)acrylates such as meth)acrylate; Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; Acrylic acid amide, methacrylic acid amide Amides such as; (meth)acrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; and vinyl chloride.

The metal to form a salt with the copolymer having pendant acid groups is selected from transition metal elements, ie elements of groups 3A to 7A, 8 and IB of the long periodic table. Among them, cobalt, nickel, copper, zinc and manganese are preferred.

The polymeric metal salt of a copolymer having pendant acid groups and a transition metal is a copolymer having pendant acid groups or an alkali metal salt thereof, and at least an equivalent amount of a metal oxide, hydroxide, chloride, or sulfide. produced by simultaneously reacting a metal compound, such as a basic carbonate, with at least an equivalent amount of a monobasic organic acid, or by reacting a copolymer having pendant acid groups with a metal salt of a monobasic organic acid. can do. Furthermore, as another method, a monomer having an acid group and a monobasic organic acid are ionically bonded to the same metal atom, and the metal salt monomer is converted into a monomer having no acid group. It can also be produced by copolymerizing with.

The monobasic organic acids used here can serve as ligand ions for the final polymeric metal complex resin; examples include acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, and oleic acid. , monocarboxylic acids such as naphthenic acid, chloroacetic acid, fluoroacetic acid, abietic acid, phenoxyacetic acid, valeric acid, dichlorophenoxyacetic acid, benzoic acid, naphthoic acid; benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalene Examples include monosulfonic acids such as sulfonic acid and P-phenylbenzenesulfonic acid.

A preferred method for producing the polymeric metal salt is the method disclosed by the present inventors in JP-A-63-128008. This method involves simultaneously reacting a metal salt of a low-boiling basic acid and a high-boiling basic acid to a copolymer having pendant acid groups, and reacting the copolymer pendant acid ion and the high-boiling basic acid to the same metal atom. This is a method for obtaining a polymeric metal salt in which ions are ionically bonded. For example, by subjecting a pendant acid group-containing copolymer copper hediacetate to a thermal reaction with naphthenic acid, a polymeric metal salt in which pendant acid ions and naphthenic acid ions of the copolymer are ionically bonded to copper atoms can be obtained.

The polymeric metal salt resin thus obtained has a pseudo-crosslinked structure due to association as described above, and therefore the viscosity of the solution is relatively high. However, according to the present invention, by adding a component to serve as a ligand to the solution of the polymeric metal salt and forming a complex, the viscosity can be significantly reduced, and when it is made into a paint, the rate of wear of the paint film and the elution of metal ions can be reduced. The amount becomes more stable over time.

A component that becomes such a ligand has oxygen as a coordinating atom,
It is an organic compound containing nitrogen or sulfur. Nitrogen compounds include amines and nitriles (cyano compounds), oxygen compounds include alcohols, phenols, aldehydes, ketones, and carboxylic acids, and sulfur compounds include 1,000-ols, thiophene compounds, These include sulfonic acid esters, thiocarbamate compounds, and isothiocyanate compounds.

The ligand compounds that can be used in the present invention are not limited to monodentate ligands. - It is also possible to use bidentate or higher ligands having a plurality of the same or different coordinating atoms in the molecule. Furthermore, the basic organic acid ion forming the polymeric metal salt, such as glycine, may have an atomic group serving as another ligand.

Examples of compounds that can be used as ligands include primary, secondary and tertiary alkylamines such as mono- and tri-n-propylamine, cyclic alkylamines such as piperidine, piperazine, ethylene diamine, etc. Alkylene diamines, alkanolamines such as mono-, di- and triethalamines, cyano compounds such as isophthalonitrile, urea, thiourea, N-(34
-dichlorophenyl)-N"-methoxy-N"methylurea, N-(3,4-dichlorophenyl)N"N"-
Substituted ureas such as dimethylurea, butyl alcohol,
Alcohols such as octyl alcohol and geraniol, phenols such as hydroquinone, hydroquinone monomethyl ether, nonylphenol, and BHT, aldehydes such as acetaldehyde and propionaldehyde F', acetylacetone, acetophenone, and 2-amino 3-chloro-14-naphthoquinone. Ketones such as acetic acid,
propionic acid, benzoic acid, lactic acid, malic acid, citric acid,
These include carboxylic acids such as tartaric acid and gleason, thiophene and its derivatives, para-toluenesulfonic acid n-propyl ester, sulfur-containing compounds such as mercaptohendithiazole, dimethyldithiocarbamate, and benzene thiocyanate. For use as a vehicle in antifouling paints, components may also be selected in which the ligand itself acts as an antifouling agent. These ligands are used in such a way that the sum m of the coordination atoms of all the ligands per central metal atom is at least 2, and at most is equal to the coordination number of the central metal atom minus IC2. . For example, if the coordination number of the central metal atom is 4, if all the ligands are monodentate, 2 to 3 moles of the ligand will be used per central metal atom, In this case, for example, 1 mol of distenographic ligand or 1 mol of distenographic ligand and 1 mol of monodentate ligand can be used. It is permissible to use a larger amount of the ligand as long as it does not cause cracks or coating defects such as blistering during immersion in water. At this time, the amount that can be used varies depending on the type of ligand, but (n-1
) Can be used up to X4.

The polymeric metal complex resin of the present invention contains 5 to 80% by weight, preferably 20 to 70% by weight of the repeating unit (a) containing a pendant acid group bonded to a metal complex, and other ethylenically unsaturated monomers. The repeating unit (b) corresponding to 95 to 20% by weight, preferably 80 to 30% by weight. If the repeating unit (a) is too large, the coating film will wear out quickly and will be consumed in a short period of time, whereas if it is too small, self-polishing action cannot be expected. The number average molecular weight of the resin is 2,000 to 100,000, preferably 4,
000 to 40.000.

If the molecular weight is too low, film-forming properties will be poor, while if the molecular weight is too high, it will be difficult to form into a coating or the hydrolyzability of the coating will be reduced.

However, the polymer metal complex resin of the present invention generally has a much lower viscosity in solution than the corresponding polymer metal salt resin, and therefore can be made into a high solid resin.

Further, the resin of the present invention is preferably designed to contain 0.3 to 20% by weight, preferably 0.5 to 15% by weight of the complexed metal.

The present invention will be explained in detail below with reference to production examples and examples. In these, "Part J" and "%" are based on weight unless otherwise specified.

Preparation Example 1 of Pendant 4 Varnish 120 parts of xylene and 30 parts of n-butanol were added to a four-hole flask equipped with a stirrer, a reflux condenser, and a dropping funnel.
Maintain at 110-120'C. To this ethyl acrylate 6
A mixed solution consisting of 0 parts of acrylic acid, 25 parts of 2-ethylhexyl acrylate, 15 parts of acrylic acid, and 2 parts of abbisisobutyronitrile was added dropwise over a period of 3 hours, and the temperature was maintained at the same temperature for 2 hours after the addition.

The solid content of the obtained varnish was 39.8%, and the solid content acid value was 20.
It was 0 mgKOR/g.

Production Example 2 To the same flask as Production Example 1, 100 parts of xylene and n
- Charge 20 parts of butanol and maintain at 100-110°C. To this, 25.7 parts of acrylic acid, 57 parts of ethyl acrylate
．． A mixed solution consisting of 8 parts of methyl methacrylate, 16.5 parts of azobisisobutyronitrile, and 3 parts of azobisisobutyronitrile was added dropwise over a period of 1 hour, and the temperature was maintained for 2 hours after the addition. The solid content of the obtained varnish was 39.6%.

The acid value of the resin solid content was 200 ■KOH/g.

Production Example 3 To the same flask as Production Example 1, 100 parts of xylene and n
- Charge 20 parts of butanol and maintain at 100-110°C. To this was added 4 parts of a mixed solution consisting of 7.7 parts of methacrylic acid, 64.4 parts of methyl methacrylate, 28 parts of 2-ethylhexyl acrylate, and 3 parts of azobisisobutyronitrile.
It takes time to drop the solution, and after dropping, it is kept at the same temperature for 2 hours.

The solid content of the obtained varnish was 39.8%, and the solid content acid value was 5.
It was 0 mgKOH/g.

Production Example 4 To the same flask as Production Example 1, 100 parts of xylene and n
- Charge 20 parts of butanol and maintain at 100-110'C. A mixed solution consisting of 38.5 parts of acrylic acid, 50.9 parts of ethyl acrylate, 10.6 parts of n-butyl acrylate, and 3 parts of azobisisobutyronitrile was added dropwise to this over a period of 4 hours. The temperature was then maintained for 30 minutes. Thereafter, a liquid mixture consisting of 20 parts of xylene, 10 parts of n-butanol, and 0.5 parts of azobisisobutyronitrile was added dropwise over a period of 1 hour, and the temperature was maintained at the same temperature for 2 hours after the addition. The solid content of the obtained varnish was 39.4%, and the solid content acid value was 300 n.
agKOH,/g.

11 Hiroshi Production Example 5 of Rowanis 100 parts of the varnish of Production Example 1, 20 parts of naphthenic acid, and 7 parts of copper hydroxide (■) were added to a four-row flask equipped with a stirrer, a reflux condenser, and a decanter, and the mixture was heated to 120° The temperature was raised to C and kept at the same temperature for 2 hours, during which time the water (2.5 g) produced was distilled off. The solid content of the obtained green varnish A was 51.3%,
The viscosity was 2.2 poise. Take a part of varnish A,
The resin was precipitated with white spirit, and the copper content was determined to be 6.8% by fluorescent X-ray method.

Production Example 6 Into the same flask as in Production Example 5, 100 parts of the varnish of Production Example 2, 25.9 parts of zinc (II) acetate, 40.3 parts of oleic acid, and 120 parts of xylene were charged, heated to 120°C, and reacted. The acetic acid produced as the process progresses is distilled off together with the solvent. The reaction continued until no acetic acid was detected in the distilled solvent. The resulting varnish B had a solid content of 55.3% and a viscosity of R-3.

Production Example 7 To the same flask as Production Example 5, 100 parts of the varnish of Production Example 3, 7.4 parts of copper (I[) propionate, 10 parts of naphthenic acid, and 20 parts of deionized water were added, and heated to 100 °C. The propionic acid produced as the reaction progressed was distilled off together with water. The reaction continued until no water or propionic acid distilled out. The solid content of the obtained varnish C was 52.3%,
The viscosity was P.

Production Example 8 Into the same flask as Production Example 5, 100 parts of the varnish of Production Example 3, 8.1 parts of manganese(II) acetate, and 7.8 parts of 2.4 dichlorophenoxyacetic acid were charged, heated to 70°C, and heated under reduced pressure. The acetic acid produced below was distilled off, and after the reaction was completed, 95 parts of xylene was added. The resulting varnish D had a solid content of 56.3% and a viscosity of U.

Production Example 9 Into the same flask as Production Example 5, 100 parts of the varnish of Production Example 4, 37.2 parts of cobalt(III) acetate, 32.1 parts of hersateic acid, and 120 parts of xylene were charged, and heated at 120°C.
The resulting acetic acid was distilled off together with the solvent. The resulting varnish E had a solid content of 55.8% and a viscosity of N.

To the government Gold S1'' - Examples 1 to 12 and Comparative Example 1 Polymer metal salt resin varnishes A-E of Production Examples 5 to 9 and various ligand compounds were mixed in the proportions shown in Table 1, and carried out. Example 1
-12 polymer metal complex resin varnishes were obtained.

As Comparative Example 1, the polymer metal salt varnish A of Production Example 5 was used as it was.

The metal complex resin varnishes of Examples 1 to 12 and Comparative Example 1 (as clear paints) were applied to the disc rotor plate so that the dry film thickness was approximately 140 μm, and the disc plate was placed in seawater (water temperature 18 μm). ~22°C) at a constant speed (circumferential speed of about 30 nt) for 3 months day and night, and the difference in film thickness between the initial film thickness and the film thickness after the 2-month test and the worn-out film thickness of the coating film were calculated. The results are shown in Table 2.

(Hereinafter, blank space) As is clear from the above results, the degree of wear of the coating film can be arbitrarily controlled by selecting the ligand.

In the voice of death ≦“ The metal salt resin varnish of Production Example 5 was concentrated under reduced pressure to an initial viscosity of 1.
0000 centipoise, and to this were added xylene, n-propylamine, di-n-propylamine, tri-n-propylamine, octyl alcohol, and acetic acid at a ratio of 1 mol, 2 mol, and 4 mol to the metal atom, respectively, to form a varnish. Look at the change in viscosity. The results are shown in Table 3.

As is clear from Table 3, the viscosity of the varnish decreases significantly due to the ligand effect, and in order to maintain a practical paint viscosity, the solid content of 40% was the limit when no ligand was added. By utilizing the child effect, it is possible to achieve a high solidity of 50% or more.

(Leaving space below) Leaching rate - Varnishes of Examples and Comparative Examples 15X10X0.1c
The coating was applied to a PVC board of 500 mm in diameter to a dry film thickness of approximately 100 μm, and the amount of metal eluted from the coating surface into seawater over time was measured. The results are shown in Table 4 and FIG.

(Margin below) 4,

[Brief explanation of the drawing]

FIG. 1 is a graph showing changes over time in the amount of copper ions released from the varnish coatings of Example 1 and Comparative Example 1.

Claims (3)

[Claims] (1) (a) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is a hydrogen atom, methyl or alkoxycarbonyl group, R^2 is a hydrogen atom or alkoxycarbonyl group, A is an acid terminal A pendant group that is an ion, M is a transition metal element, L is an organic ligand, at least one of which is an organic acid ion, and m is 2≦m≦n-1
The integer represented by n is the coordination number of the central metal atom M. ) 5 to 80% by weight of repeating units represented by; (b) containing 95 to 20% by weight of repeating units corresponding to other ethylenically unsaturated monomers and having a number average molecular weight of 2,000
A film-forming polymeric metal complex resin comprising a copolymer having a molecular weight of 100,000 to 100,000. (2) The central metal atom M is cobalt, nickel, copper,
The film-forming polymeric metal complex resin of item 1, which is manganese or zinc. (3) The film-forming polymeric metal complex resin according to item 1 or 2, wherein the coordinating atom of the ligand L is nitrogen, oxygen, or sulfur.