JPH0768458B2 - Metal-containing resin composition and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel metal-containing resin composition and a method for producing the same, and more specifically, in the main chain of the resin, main chain terminals,
Alternatively, the present invention relates to a metal-containing resin composition in which a novel metal bond is introduced at the side chain end in the side chain, and a method for producing the same.

BACKGROUND ART In the field of ship bottom coatings and the like, attention has been focused on coating compositions that have a self-polishing effect and an antifouling effect that include as a binder a resin that is gradually hydrolyzed in an ionic atmosphere and is eluted into seawater. As such a binder resin, many resin compositions containing a metal ester bond in the molecule have been proposed. For example, Japanese Patent Application No. Sho 56-165922,
No. 58-196900 discloses a hydrolyzable polyester resin in which a large number of metal ester bonds are incorporated in the polyester main chain, but the molecular quality of the resin itself is about 20.
Since it is comparatively small at around 00, the film-forming property is poor, and there is a drawback that cracks and peeling of the coating film are likely to occur, and if the molecular weight is increased to improve the film-forming property, its hydrolyzability becomes extremely poor. If the metal ester concentration is increased,
Since the solubility in ordinary solvents is poor, it causes problems in coating, and also causes undesired results such as swelling of the coating film in seawater, and the decomposition points increase, resulting in rapid decomposition of the resin. It has been pointed out that it is eluted and it becomes difficult to control the hydrolysis rate.

On the other hand, as a resin in which a metal ester bond is introduced into a side chain portion, for example, an acrylic resin in which a trialkyl tin ester is introduced into a side chain end has been known for a long time. In this kind of resin, the organic tin part is released by the hydrolysis of the metal ester part of the side chain to generate a hydrophilic carboxyl group, and the resin is eluted only when the concentration reaches a certain critical value. It is easier to control the hydrolysis rate than a resin of the type containing a large number of metal ester bonds in the main chain. However, in order to make a stable and tough coating film, it is desirable that the resin is a polymer that does not contain a hydrophilic group as much as possible, and in order for the decomposed resin to be dissolved in water, It must be ensured that hydrophilic group concentrations above a certain critical value are provided. Therefore, usually, when producing such a resin by copolymerization of a triorganotin salt of α, β-unsaturated basic acid and an acrylic monomer, the former is set to a high concentration, for example, 55 to 75% by weight of the total weight of the monomer, and the latter is Is designed to eliminate hydrophilic monomers as much as possible. Therefore, a large amount of expensive organotin compound is required, resulting in high cost, and use of harmful tin compound is not desirable from a public health point of view.

Therefore, the inventors of the present invention have a group having a group capable of generating a hydrophilic group by hydrolysis in the side chain of the resin, and a resin excellent in film-forming property of a type that is eluted by receiving an appropriate hydrolysis in seawater. As a hydrolyzable resin that does not rely on triorganotin salts, which is expensive and is not desirable for public health use, and has the formula -XO-M-R] _X ( Where X is M is zinc, copper or tellurium atom; R is Or R ₁ is a monovalent organic residue; x is an integer of 1 to 2), and a metal-containing resin composition comprising a resin having at least one group represented by the following (Japanese Patent Application No. 60-106434), In order to further improve the antifouling performance, at least one side chain end part has the formula: (Where X is Or an aromatic residue; M is a metal atom having a valence of 2 or more; x is an integer of 1 to 2; m is an integer of 1 or more, n is 0 or an integer of 1 or more, provided that m + n + 1 is a valence of the metal M. Equally; R ₁ is a hydrocarbon residue having 1 to 10 carbon atoms; R ₂ is Or An organic acid residue having biological activity capable of being bonded to the metal atom M via R; R ₃ is at least one group represented by hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms) Resin composition (Japanese Patent Application No. 60-224168 (Japanese Patent Application Laid-Open No. 62-8416)
No. 8)), and at least one end of the side chain has the formula (Where X is Methylene group or methine group; x is an integer of 1 to 2; R ₁ is a hydrocarbon residue having 1 to 10 carbon atoms; R ₂ is Or An organic compound residue having an antifouling property, which is bonded to a tin atom via R; R ₃ is at least one group represented by hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms); Composition (Japanese Patent Application No. 60-251784 (JP-A-62-1126)
No. 69)) has been proposed. Each of these resin compositions includes, for example, a resin containing an organic acid or an alkali metal salt thereof in the side chain, a metal oxide, a hydroxide, a chloride, or a sulfide, and a monovalent organic acid having antifouling performance. Is easily produced by a method such as reacting with heat, is hydrolyzed at an appropriate rate in an ionic atmosphere such as seawater, and when the hydrophilic group concentration reaches a certain critical value, the resin itself elutes and the self-polishing effect Since the antifouling property can mainly depend on the organic acid released by hydrolysis, the metal species simply associates the antifouling compound with the highly hydrophilic resin part, or controls the hydrolysis rate. It is considered only as a part to be used, and in terms of film forming property, the resin type is acrylic resin,
It is a very useful antifouling paint resin vehicle, which can be appropriately selected from a wide range of polyester resins, alkyd resins, epoxy resins and the like and can be sufficiently satisfied.

However, in all of the conventionally proposed metal-containing resins, the bond between the resin body and the metal depends only on the metal-carboxylic acid ester bond, and such a site is easily hydrolyzed in an ionic atmosphere. However, when considering application to antifouling paints, not only the hydrolysis rate of the resin but also the elution of the decomposed resin into seawater must be taken into consideration. In this sense, it cannot be said that the conventional resin of the type that produces only a carboxyl group by hydrolysis has a sufficient elution property in seawater.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Therefore, a new type of bonding between a resin and a metal, which retains sufficient hydrolyzability in an ionic atmosphere and allows the resin after decomposition to be more easily eluted, It is an object of the present invention to provide such a metal-containing resin composition. Furthermore, a resin composition containing a metal in the main chain or side chain in such a novel binding mode, having sufficient film-forming properties and hydrolyzability in an ionic atmosphere, and capable of exhibiting a self-polishing effect and an antifouling property. It is also an object of the invention to provide It is also one of the objects of the present invention to establish an industrially advantageous method for producing such a novel metal-containing resin composition.

Means for Solving the Problems According to the present invention, the above-mentioned object is incorporated into a molecule by a bond represented by the following formula: (In the formula, M is a metal atom having a valence of 2 or more; l is an integer of 1 or more, m and n are 0 or an integer of 1 or more, respectively;
+ M + n is equal to the valence of metal M; Y is p is 0 or an integer of 1 to 5; X is However, Z is an oxygen or sulfur element; R ₁ is a hydroxyl group, halogen, Or R ₃ —Y—X— group; R ₃ is an organic group; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms), and a metal-containing resin composition comprising a polymer compound is provided. Can be achieved.

The metal-containing resin composition of the present invention is characterized by having at least one novel bond represented by the above formula in the molecule. Such a novel bond is -N = C = Z (Z is oxygen. Or the reaction of a (sulfur element) group with a hydroxide of a metal having a valence of 2 or more, or (Wherein Z is as described above; A is hydrogen or an alkali metal; p is 0 or an integer of 1 to 5) and an oxide, hydroxide, halide, inorganic acid salt or carbon of a metal having a valence of 2 or more. It is produced by the reaction of an organometallic salt of the number 1 to 10, and therefore the resin composition of the present invention is advantageously prepared by a method of carrying out the above reaction either at the end of the resin or during the resin production process. It can be manufactured. More specifically, the resin composition of the present invention can be produced by any of the following methods.

(1) Method to be carried out at the resin end portion (A) Reaction of -N = C = Z with metal hydroxide: -N = C = Z Valence of 2 or more for polymer compound having at least one terminal group. The metal hydroxide of
If desired, the resin is modified with a suitable modifier.

As the polymer compound having at least one —N═C = 0 group, various compounds such as an acrylic resin, a polyester resin, an alkyd resin, an amino resin, a polyurethane resin and an epoxy resin are known, and can be easily obtained by a known modification means. And any of them may be advantageously used in the present invention. As a metal hydroxide having a valence of 2 or more
I b (eg Cu), II a (eg Mg, Ca, Sr etc.), II b
(Eg Zn, Cd etc.), III a (eg Al, Ga etc.), I
II b (eg Sc), IV a (eg Sn, Pb), IV
b (eg Ti, Zr etc.), V a (eg Sb etc.), VI a
(Eg Se), VI b (eg Cr), VII b (eg Mn) and VIII (eg Fe, Co, Ni etc.) group metals, preferably Cu, Zn, Ni, Co, Pb, Al, S
Hydroxides of n, Mg and Ti are used and are intended to also include alkylated hydroxides such as dialkyl titanium hydroxide.

Depending on the ratio of the polymer compound having —N═C═Z group and the metal hydroxide, the formula (In the formula, Z is oxygen or a sulfur element; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms, n is 0 or an integer of 1 or more,
m is 0 or an integer of 1 or more, l is an integer of 1 or more, provided that l
+ M + n is a number equal to the valence of the metal M; M is a metal atom having a valence of 2 or more), and a resin having a bond represented by the following formula can be obtained. Treated with a monofunctional or polyfunctional modifier such as an acid, a thiocarboxylic acid, an amino acid, an organic sulfonic acid, an organic phosphoric acid or an alkali metal salt thereof, (In the formula, Z, R ₂ , n, m, l, and M are as described above; R ′
₁ is Or R ₃ —Y—X— group; R ₃ is an organic group; Y is p is 0 or an integer of 1 to 5; X is A resin having is obtained.

(B) With at least one polymer compound, metal oxide, hydroxide, halide, inorganic acid salt or carbon number 1
Reactions of ~ 10 organometallic salts: As the polymer compound having at least one of, for example, various resins obtained by reacting water with a polymer compound having a —N═C═Z group, a compound having two or more amino acid groups (for example, cystine) and a bifunctional alcohol. The polycondensation product of 1), a polymer compound derived from a compound having an amino acid group and a reactive functional group (for example, aspartic acid, etc.) and the like are optionally used. When such a polymer compound is reacted with an oxide, a hydroxide, a halide, an inorganic acid salt or an organic metal salt having a carbon number of 1 to 10 having a valence of 2 or more as described above, depending on the use ratio thereof, formula (Wherein Y, X, M, 1, n, m, and R ₂ are as described above; R ″ ₁ is a hydroxyl group or halogen), and a resin having an isocyanate, a thioisocyanate, a carvone is optionally added. When treated with monofunctional or polyfunctional modifiers such as acids, thiocarboxylic acids, amino acids, organic sulfonic acids, organic phosphoric acids or their alkali metal salts (Wherein R ′ ₁ , Y, X, R ₂ , m, n, l, and M are as described above), a metal-containing resin composition having a bond is obtained.

(2) Method carried out in the resin manufacturing process (c) Polyfunctional Reaction of contained compound with metal oxide, hydroxide, halide, inorganic acid salt or organic metal salt having 1 to 10 carbon atoms: Examples of polyfunctional isocyanate include tolylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, undecamethylene diisocyanate, cyclohexane diisocyanate, phenyl diisocyanate, toluene diisocyanate, tolylene triisocyanate, polyol adduct of diisocyanate, diisocyanate polymer, etc., as a polyfunctional carbamic acid, For example, compounds obtained by allowing water to act on the above polyfunctional isocyanates or thioisocyanates are also used as polyfunctional isocyanates. The Amino Acids, e.g. cystine, or amino acids having a functional group and an amino acid group (such as serine, threonine, cysteine, methionine, etc. Asupafugin acid) such as a polyfunctional amino acids derived from the like. Moreover, as oxides, hydroxides, halides, inorganic acid salts (for example, nitrates, sulfates, etc.) of metal having a valence of 2 or more, and organic metal salts having 1 to 10 carbon atoms (for example, dibutyltin oxide) are applicable. Any compound known in the art may be used. By reacting the polyfunctional compound with a metal salt or the like, for example, reacting with —N═C═Z and a metal hydroxide, And the reaction of metal oxides, hydroxides, halides, inorganic acid salts or organic metal salts having 1 to 10 carbon atoms, (Wherein Y, X, M, R ″ ₁ , R ₂ , M, m, and n are as described above, respectively, provided that l is an integer of 2 or more), and the terminal portion is Or R ″ _1. Either type of resin is obtained. If desired, the resin may be added with water, alcohol, thioalcohol, isocyanate, thioisocyanate, organic carboxylic acid, organic sulfonic acid, organic phosphoric acid, When treated with a monofunctional or polyfunctional modifier such as carbamic acid or amino acid, (In the formula, Y, X, M, R ₂ , m, and n are as described above, 1 is an integer of 2 or more, and R ₁ is Alternatively, a resin having a group represented by R ₃ —Y—X— group; R ₃ is an organic group) is obtained.

(D) A method of introducing a —Y—X—M bond into a resin constituent and then producing a resin: (i) a polymerizable ethylene bond and a formula —N═C = Z, A compound having at least one group represented by and a valence of 2
The above metal oxides, hydroxides, halides, inorganic acid salts, or organic metal salts having 1 to 10 carbon atoms, and optionally a low-molecular or high-molecular isocyanate, thioisocyanate, carboxylic acid, thiocarboxylic acid , A carboxylic acid, an amino acid, an organic sulfonic acid, an organic phosphoric acid, and a polymerizable monomer obtained by a reaction with a monofunctional or polyfunctional compound selected from alkali metal salts of these organic acids, or a copolymerization of the monomer with another monomer. A method for obtaining a metal-containing resin composition by polymerizing a polymerizable monomer. With the polymerizable ethylene bond used in this method Examples of the compound having at least one of (In the formula, R is hydrogen or a methyl group; A is a direct bond, Or a phenylene group which may contain a substituent; a vinyl isocyanate represented by R ¹ and R ² is an alkylene group; a corresponding vinylcarbamic acid obtained by reacting this with water; a hydroxyalkyl acrylate or a methacrylate and a polyfunctional isocyanate (for example, A compound containing one or more ethylene bonds and one or more isocyanate groups obtained by the reaction of a diisocyanate polyol adduct, a diisocyanate polymer, etc .; a corresponding carbamic acid derivative; a compound having a hydroxyl group in an amino acid (eg, serine, threonine) and the above formula A reaction product of a vinyl isocyanate represented by: a reaction product of an amino acid having a carboxyl group (for example, cystine, aspartic acid, etc.) with glycidyl acrylate, glycidyl methacrylate, and the like, Necessary depending be readily produced by one skilled in the art. By the reaction of the above-mentioned raw material compounds, at least one polymerizable ethylene bond and a formula (In the formula, M is a metal atom having a valence of 2 or more; l is an integer of 1 or more, m and n are 0 or an integer of 1 or more, respectively, and l +
m + n is equal to the valence of the metal M; Y is p is 0 or an integer of 1 to 5; X is However, Z is an oxygen or sulfur element; R ₁ is a hydroxyl group, halogen, Alternatively, a polymerizable monomer having a bond represented by R ₃ —Y—X— group, R ₃ is an organic group; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms) is obtained in the present invention. By polymerizing the monomer alone, or by polymerizing the monomer with another copolymerizable monomer by a conventional method, at least one side chain portion or cross-linking point portion of the vinyl-based resin can be formed by the formula (Wherein Y, X, M, R ₁ , R ₂ , l, m, and n are as described above), a resin having a bond is produced.

(Ii) Formula -N = C = Z, (Wherein Z is an oxygen or sulfur element; A is hydrogen or an alkali metal; p is 0 or an integer of 1 to 5), a compound having at least one group, an oxide of a metal having a valence of 2 or more, and water. Oxides, halides, inorganic acid salts or organic metal salts having 1 to 10 carbon atoms, and a polymerizable ethylene bond, Metal-containing resin composition obtained by reacting a polymerizable monomer alone obtained by reaction with a compound having at least one sulfonic acid group, phosphoric acid group, or alkali metal salt thereof, or by polymerizing the monomer with another copolymerizable monomer How to get things. The method involves the presence of a polymerizable ethylene bond in the organic acid used as a modifier, The metal-containing vinyl resin composition according to the present invention can be obtained by the same reaction mode as in (i), except that it is not present in the compound having

The polymerizable unsaturated organic acid used in the above method is, for example, methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid, acid phosphooxypropyl methacrylate,
3-Chloro-2-acidphosphooxypropyl methacrylate, acidphosphooxyethyl methacrylate, itaconic acid, maleic acid (anhydrous), monoalkyl itaconate (eg methyl, ethyl, butyl, 2-ethylhexyl etc.), monomaleic acid Alkyl (eg, methyl, ethyl, butyl, 2-ethylhexyl, etc.); Half ester of OH group-containing polymerizable unsaturated monomer and acid anhydride, eg, 2-hydroxyethyl (meth) acrylate, succinic anhydride, maleic anhydride , Half-esters such as phthalic anhydride, etc., and one kind or a combination of two or more kinds thereof can be used.

In the present invention, when a -N = C = Z group remains as a resin end group, the obtained resin is optionally modified with water, alcohol, thioalcohol, organic acid, etc. When R _{1 of} is a hydroxyl group or a halogen atom, it may be optionally modified with an isocyanate, a thioisocyanate, a carboxylic acid, a thiocarboxylic acid, a carbamic acid, an amino acid, an organic sulfonic acid, an organic phosphoric acid or an alkali metal salt of those organic acids. If desired, these modifiers can be used as a polyfunctional compound for the purpose of further polymerizing. As such a modifier, an extremely wide range of compounds, for example, any organic acid is used. For example, higher fatty acids such as oleic acid, stearic acid and balmitic acid, various fatty acids such as coconut oil, bran oil, soybean oil and linseed oil, etc. Naphthenic acid, versatic acid, pivalic acid, neoic acid,
Linear or branched acids such as 2-ethylhexanoic acid and various synthetic fatty acids are used. However, for antifouling paints, it is particularly preferable that such a modifying agent is a monovalent organic acid having antifouling properties, specifically, the following organic acids.

With: alicyclic carboxylic acids such as thiaum-glicic acid, hydronocarpsic acid; salicylic acid, cresotic acid, naphthoic acid, p-oxybenzoic acid, benzoic acid, mandelic acid, dibromosalicylic acid, cinnamic acid, Caprochloronic acid,
Nitrobenzoic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5
-Aromatic carboxylic acids such as trichlorophenoxyacetic acid, nitronaphthalenecarboxylic acid, aspirin and nicotinic acid; lactone-based carboxylic acids such as puruvic acid and bruvic acid; uracil-4-carboxylic acid and 5-fluorouracil-4 Carboxylic acids, uracil derivatives such as uracil-5-carboxylic acids; carboxylic acids having a penicillin skeleton such as penicillin U, ampicillin, penicillin BT, penicillic acid, penicillin G, penicillin O; other sarcomycin, chloramphenicol, Valiotin, trypacidine, rifamycin B, luzonsomycin and the like.

The alcoholic hydroxyl group-containing bioactive substance can also be used by introducing a carboxylic acid by half-esterification with an acid anhydride (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride). These alcoholic hydroxyl group-containing bioactive substances include testosterone, uridine, thymidine, lementhol, cinnamic alcohol, benzyl alcohol, maltol, linalool, dimethylbenzylcarbinol, and rosinol.

Having: There are dithiocarbamates such as dimethyldithiocarbamate.

With: Sulfur-containing aromatic compounds such as 1-naphthol-4-sulfonic acid, paraphenylbenzenesulfonic acid, β-naphthalenesulfonic acid, and quinolinesulfonic acid.

Having: triethylpyrophosphate, dimethylamino phosphate, and other various organic phosphoric acid compounds.

With an S-bond: And a compound having

And thiocarboxylic acids having

Those having a —O— bond: phenol, cresol, xylenol, thymol, carvacrol, eugenol, phenylphenol, benzylphenol, guaiacol, butylstilbene,
(Di) nitrophenol, nitrocresol, methyl salicylate, benzyl salicylate, (mono, di, tri, tetra, penta) chlorophenol, chlorocresol,
Chloroxylenol, chlorothymol, p-chloro-O
-Cyclohexylphenol, p-chloro-O-cyclopentylphenol, p-chloro-On-hexylphenol, p-chloro-O-benzylphenol, p-
Besides phenols such as chloro-O-benzyl-m-cresol, there are β-naphthol, 8-hydroxynoline and the like.

Although these are typical examples of organic acids that can be used, the present invention is not limited to such organic acids.For example, a sample is put in a recess of a test plate having a recess, and seawater aquatic organisms on a wire net are present. Any organic acid can be used as long as it is a compound having an antifouling property by a simple test such as examining the adhesion state.

The metal-containing resin composition according to the present invention thus obtained has the formula (Wherein _{each of} Y, X, M, R ₁ , R ₂ , m, n, and l is as described above), at least one novel bond is contained in the molecule, and excellent film formation is achieved. Not only is it provided as a resin composition, but the -Y-X-M bond in such a resin is easily hydrolyzed in an ionic atmosphere. Is decomposed into a resin part having a zwitterionic group and a metal compound part, and this resin part having a zwitterionic group elutes much more easily than a resin having a conventional carboxyl group. Is extremely useful as Further, since it can be modified with an organic acid having antifouling property, the modifier residue represented by R ₁ is also released by hydrolysis, and excellent antifouling property can be expected together with metal ions. In the resin of the present invention, a carboxyl group, an isocyanate group, a hydroxyl group, an epoxy group and the like can be appropriately incorporated and left, so that, for example, a curing agent component such as an epoxy compound, polyamine, polyol, melamine, or an isocyanate compound and If desired, it can be used as a curing agent resin in combination with a curing accelerator.

Hereinafter, the present invention will be described with reference to examples. Unless stated otherwise, parts and percentages are by weight.

Varnish Production Example 1 80 parts of xylene and 10 parts of methyl isobutyl ketone were added to a four flask equipped with a stirrer, a dropping funnel, and an N ₂ gas introduction tube, and the temperature was raised to 80 to 90 ° C. Ethyl acrylate in this solution
44.7 parts, methyl methacrylate 35.4 parts, methacrylic acid 8.6
Part, 2-ethylhexyl acrylate (12.3 parts), and azobisisobutyronitrile (1.4 parts) are added dropwise over 3 hours, and then the mixture is kept warm for 30 minutes. Next, a mixed solution of 10 parts of methyl isobutyl ketone and 0.5 part of azobisisobutyronitrile was added dropwise over 30 minutes, and then the temperature was kept for 2 hours. The obtained varnish A has a solid content of 50.1%, a number average molecular weight of 13,000,
The solid acid value was 56.1 mg KOH / g.

Varnish Production Example 2 80 parts of xylene and 10 parts of methyl isobutyl ketone are added to the same production apparatus as in the varnish production example 1, and the temperature is raised to 100 to 110 ° C. A mixture of 12.3 parts of methyl methacrylate, 21.6 parts of acrylic acid, 66.1 parts of ethyl acrylate, and 2 parts of azobisisobutyronitrile was added dropwise to this solution over 3 hours and kept warm for 30 minutes. Then, a mixture of 10 parts of methyl isobutyl ketone and 0.3 part of azobisisobutyronitrile was added dropwise over 30 minutes, and then the mixture was kept warm for 2 hours. The solid content of this varnish B was 49.2%.

Varnish Production Example 3 4 equipped with decanter, stirrer, N ₂ gas introduction pipe, cooler
5 parts xylene, 63.4 parts phthalic anhydride in a two-necked flask,
1,6-hexanediol 50.6 parts, dibutyltin oxide
After adding 0.02 part, the reaction was carried out at 150 to 200 ° C, and 6.9 g of dehydration was confirmed. After cooling, 100 parts of methyl isobutyl ketone was added to obtain a varnish having a solid content of 50.1% and a varnish acid value of 53 mgKOH / g.

Varnish Production Example 4 Using the same apparatus as in Varnish Production Example 3, 5 parts of xylol, 56.3 parts of phthalic anhydride, 50.6 parts of 1,6-hexanediol and 0.02 part of dibutyltin oxide were added to a four-neck flask.
The reaction was carried out while removing water produced at a reaction temperature of 150 to 200 ° C. The reaction was followed by the dehydration amount, and a dehydration amount of 6.8 g was confirmed. Then it was cooled to 170 ° C. and 95 parts of methyl isobutyl ketone were added. The varnish D had a solid content of 49.8% and a varnish acid value of 0.04 mgKOH / g.

Varnish Production Example 5 Using the same apparatus as in Varnish Production Example 1, 80 parts of xylene was added to a 4-neck flask and the temperature was raised to 80 to 90 ° C. In this, isocyanyl ethyl methacrylate 28.8 parts, ethyl acrylate 44.6
Part, methyl methacrylate 13.8 parts, 2-ethylhexyl acrylate 12.8 parts, and azobisisobutyronitrile 1.4 parts were added, and the mixture was added dropwise over 3 hours and kept warm for 30 minutes. Next, 20 parts of methyl isobutyl ketone and 0.3 parts of azobisisobutyronitrile were added dropwise over 30 minutes, and then 2 parts were added.
I kept it warm for an hour. The solid content of the obtained varnish E was 49.8%.

Varnish Production Example 6 2 g of water was added to 100 g of the varnish E produced in Production Example 5 of varnish 60
Warm at 2 ° C for 2 hours. This is varnish F.

Monomer Production Example 1 200 parts of xylene, 125 parts of serine, 72 parts of isocyanylethyl methacrylate, and 0.05 parts of hydroquinone were added to a four-necked flask equipped with a cooling tube, a stirrer, and an air introduction tube, and 20-40 ° C.
It was made to react with. The reaction was followed by an IR spectrum, 2200-23
This process was repeated until the peak appearing around 00 cm ^-1 disappeared to obtain a monomer solution A.

Monomer Production Example 2 100 parts of methyl isobutyl ketone, 72 parts of isocyanylethyl methacrylate, 100 parts of zinc hydroxide, 100 parts of naphthenic acid and 0.1 part of hydroquinone were placed in a four-neck flask while air bubbles were generated in the apparatus of varnish preparation example 3. 60-80
The temperature was raised to ℃ and kept for 30 minutes. Thereafter, the temperature was raised to 110 ° C., about 9 g of water produced was removed, and filtration and purification were performed. The IR spectrum confirmed the disappearance of NCO absorption and the presence of vinyl groups and zinc salts. This is designated as Monomer Solution B (72% active ingredient).

Monomer Production Example 3 decanter, stirrer, air inlet tube, the monomer solution A100 parts into a four-necked flask equipped with a condenser, aluminum diisopropylate oxy hydroxide _{(HO-Al-OC 3 H} 7) 80
Part, 2,4-dichlorophenoxyacetic acid 52 parts, 40-60
The temperature was maintained at 30 ° C. for 30 minutes, the temperature was raised to 110 ° C. while removing isopropyl alcohol, and the temperature was maintained for 30 minutes. This is designated as monomer solution C (75% active ingredient).

Example 1 65 parts of xylene is added to a four-necked flask equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a dropping funnel, and the temperature is raised to 90 to 100 ° C. A mixture of 74 parts of a monomer solution, 25 parts of methyl methacrylate, 25 parts of ethyl acrylate and 1.2 parts of azobisisobutyronitrile was added dropwise to this solution over 3 hours, and then the mixture was kept warm for 30 minutes. Then, a mixture of 5 parts of xylene, 5 parts of n-butanol and 0.3 part of azobisisobutyronitrile was added to 30 parts of the mixture.
The mixture was added dropwise over a period of 1 minute and then kept warm for 2 hours. The resulting varnish 1 had a solid content of 48.7% and a viscosity of 4.7 poise.
This varnish was filtered and purified by reprecipitation with n-hexane, and the metal in the resin was quantified by the fluorescent X-ray method. As a result,
There was 7.4% Zn.

Example 2 Using the same apparatus as in Example 1, 65 parts of xylene is added to a four-necked flask and the temperature is raised to 95 to 110 ° C. A mixture of 100 parts of monomer C, 10 parts of 2-ethylhexyl acrylate, 25 parts of ethyl acrylate and 2 parts of azobisisobutyronitrile was added dropwise to this solution over 3 hours, and then the mixture was kept warm for 30 minutes. Next, a mixture of 10 parts of methyl isobutyl ketone and 0.5 part of azobisisobutyronitrile was added dropwise over 30 minutes,
After that, it was kept warm for 2 hours. The resulting varnish 2 has a solid content of 4
The viscosity was 9.7%, the viscosity was 8.6 poise, and the Al% in the resin was 12.6%.

Example 3 100 parts of varnish A, 2.5 g of aminobutyric acid, and 9 parts of diisopropyl alcoholate of dioctyl titanium were added using the same apparatus as in Production Example 3 of the varnish, the temperature was raised to 40 to 60 ° C., the temperature was kept for 30 minutes, and then cooled. The resulting varnish 3 had a solid content of 50.2% and a viscosity of 4.8 poise. The Ti% in the resin was 2.2%.

Example 4 100 parts of varnish D, 16 parts of copper hydroxide, and 52 parts of lysino diisocyanate were added using the same apparatus as the varnish manufacturing example 3, and it kept at 110 degreeC for 4 hours. Then xylene 38 parts, n-butanol 30
Diluted in parts. The resulting varnish 4 had a solid content of 50.2% and a viscosity of 7.2 poise. Cu% in the resin was 8.8%.

Example 5 Using the same apparatus as in Production Example 3 of varnish, 5 parts of xylol, 94 parts of aspartic acid, 90 parts of 1,6-hexanediol and 0.05 part of dibutyltin oxide were added to a four-necked flask, and
The reaction was carried out while removing water produced at 0 to 250 ° C. When the dehydration amount reached 25 cc, the mixture was cooled, 16 parts of magnesium diisopropyl alcoholate was added, and the mixture was diluted with methyl isobutyl ketone. The solid content of the obtained varnish 5 is 48.6.
%, The viscosity was 7.9 poise, and the Mg% in the resin was 1.7%.

Example 6 Using the same apparatus as in Varnish Production Example 3, 100 parts of varnish E, 20 parts of aluminum triisopropyl alcoholate and 34 parts of 3-chlorophenylcarbamic acid were added to a four-necked flask and reacted at 40 to 80 ° C. for 1 hour. Diluted with methyl isobutyl ketone. The resulting varnish 6 had a solid content of 46.8% and a viscosity of 7.1 poise.

Example 7 A varnish 7 having a solid content of 49.8% and a viscosity of 7.1 poise was obtained in the same manner as in Example 4 except that 14 parts of manganese hydroxide was used instead of the copper hydroxide of Example 4. Mn% in this resin is 8.2
%Met.

Example 8 A varnish 8 having a solid content of 49.7% and a viscosity of 6.4 poise was obtained in the same manner as in Example 4 except that 15 parts of cobalt hydroxide was used instead of the copper hydroxide of Example 4. Co% in this resin is 8.6
%Met.

Example 9 In the apparatus of Example 3, 100 parts of varnish F, 12 g of dimethyldithiocarbamic acid and 18 g of copper diisopropyl alcoholate were added, and the mixture was kept at 60 ° C. for 1 hour. The solid content of the obtained varnish 9 is
The viscosity was 52.3% and the viscosity was 8.2 poise.

Example 10 To a four-necked flask equipped with a cooling tube, a stirrer, a decanter, and a nitrogen introducing tube, 100 parts of varnish B, 50 parts of dibutyltin diisopropyl alcoholate, and 18 parts of proline were added, and the mixture was mixed at 40-60 ° C. for 1 hour.
Reacted for hours. The solid content of the obtained varnish 10 is 55.7%,
The viscosity was 5.8 poise.

Example 11 100 parts of varnish F, benzene sulfonic acid in the apparatus of Example 4
A varnish 11 having a solid content of 48.6% and a viscosity of 6.6 poise was obtained in the same manner as in Example 4 except that 16 parts and 10 parts of nickel hydroxide were used. The Ni% in this resin was 8.8%.

Example 12 Using 11 parts of O-dimethylphosphoric acid instead of benzenesulfonic acid of Example 11, a varnish 12 having a solid content of 47.3% and a viscosity of 6.2 poise was obtained. The Ni% in this resin was 8.9%.

Comparative Example 1 Comparative varnish 1 was obtained in the same manner as in Example 10 except that 42 parts of oleic acid was used instead of proline in Example 10.

Comparative Example 2 Phthalic anhydride 104 instead of aspartic acid of Example 5
Comparative varnish 2 was obtained in the same manner as in Example 5 except that parts were used.

Comparative Examples 3 to 4 Varnish B is comparative varnish 3 and varnish F is comparative varnish 4.

Examples 13 to 24 and Comparative Examples 5 to 8 Resin elution amount test and results Varnishes 1 to 1 obtained on Examples 1 to 12 on a glass plate of 30 x 50 mm.
About 1 g of the comparative varnishes 1 to 4 obtained in 12 and Comparative Examples 1 to 4 were applied and dried. The coated plate was dipped in a buffer solution of pH = 9.2, and the weight change after 30 days was observed. The results are shown in Table 1.

As is clear from Examples 13 to 24 and Comparative Examples 5 to 8, the resins obtained according to the present invention decompose and elute under an ionic atmosphere. On the other hand, the resin composed of the metal carboxylate has a low elution amount as is clear in Comparative Examples 5 and 6, and the elution amount of the resin before containing the metal is extremely large. This is because it does not take a process and is merely eluted.

As described above, the resin obtained in the present invention has a larger elution amount than the conventional one, in other words, the metal amount can be reduced to obtain the same elution amount as the conventional one.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C09D 143/00 PGM 201/02 PDE (72) Inventor Kiyoaki Higo 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka No. 19 Japan Paint Co., Ltd. (72) Inventor Hiroshi Takahashi 19-17 Ikedanaka-cho, Neyagawa City, Osaka Prefecture Japan Paint Co., Ltd.

Claims (11)

[Claims] 1. A bond represented by the following formula in a molecule: (In the formula, M is a metal atom having a valence of 2 or more selected from Zn, Al, Ti, Cu, Mg, Mn, Co, Sn, and Ni: 1 is an integer of 2 to 4, and m and n are 0 or 1 respectively. Integer above, where 1 + m + n is metal M
Is equal to the valence of: Y is However, Z is an oxygen or sulfur element; R ₁ is a hydroxyl group, Or R ₃ —Y—X— group, R ₃ is an organic group; R ₂ is an acrylic resin, polyester resin or alkyd resin having at least one of oxygen or a hydrocarbon residue having 1 to 10 carbon atoms and a solvent Metal-containing resin composition. 2. The composition according to claim 1, wherein R ₃ is a high molecular organic residue. 3. The composition according to claim 1, wherein R ₃ is a low molecular weight organic residue. 4. The composition according to claim 1, wherein R ₃ is a monovalent organic residue. 5. The composition according to claim 1, wherein R ₃ is a polyvalent organic residue. 6. The composition according to claim 1, wherein R ₁ is an organic acid residue having bioactivity. 7. The formula in the molecule (Wherein Z is oxygen or sulfur element; A is hydrogen or alkali metal) and an acrylic or polyester polymer compound having at least one group and Zn, Al, Ti, Cu, Mg, Mn, C
Oxides of metals with a valence of 2 or more selected from o, Sn and Ni,
By reacting with a hydroxide, an inorganic acid salt or an organic metal salt having 1 to 10 carbon atoms, if desired, water, alcohol, thioalcohol, isocyanate, thioisocyanate, carboxylic acid, thiocarboxylic acid, carbamic acid, amino acid, organic sulfonic acid And modified with a monofunctional or polyfunctional compound selected from the group consisting of organic phosphoric acid,
A bond represented by the following formula in the molecule (In the formula, M is a metal atom having a valence of 2 or more selected from Zn, Al, Ti, Cu, Mg, Mn, Co, Sn, and Ni; 1 is an integer of 2 to 4, and m and n are 0 or 1 respectively. Integer above, where 1 + m + n is metal M
Is equal to the valence of; Y is However, Z is oxygen or a sulfur element; R ₁ is a hydroxyl group; Or R ₃ —Y—X— group, R ₃ is an organic group; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms) A metal-containing resin composed of an acrylic or polyester polymer compound A method for producing a composition. 8. A compound containing two or more groups represented by the formula —N═C = Z (where Z is oxygen or sulfur element) in the molecule and a metal hydroxide having a valence of two or more are used. A method according to claim 7. 9. The method according to claim 8, wherein a low molecular weight or high molecular weight polyol is further present. 10. (a) Polymerizable ethylene bond and formula (Wherein Z is an oxygen or sulfur element; A is hydrogen or an alkali metal), and a low-molecular compound having at least one group respectively, (b) Zn, Al, Ti, Cu, Mg, Mn, Co, Sn Oxides, hydroxides, inorganic acid salts or organic metal salts having 1 to 10 carbon atoms having a valence of 2 or more selected from Ni, Ni, and (c) optionally added low-molecular or high-molecular isocyanate, Polymerizable monomer alone obtained by reaction with monofunctional or polyfunctional compound selected from thioisocyanate, carboxylic acid, thiocarboxylic acid, carbamic acid, amino acid, organic sulfonic acid, organic phosphoric acid, and alkali metal salts of these organic acids Or a bond represented by the following formula in the molecule, which is characterized by polymerizing the monomer and another copolymerizable monomer. (In the formula, M is a metal atom having a valence of 2 or more selected from Zn, Al, Ti, Cu, Mg, Mn, Co, Sn, and Ni; 1 is an integer of 2 to 4, and m and n are 0 or 1 respectively. Integer above, where 1 + m + n is metal M
Is equal to the valence of; Y is However, Z is oxygen or a sulfur element; R ₁ is a hydroxyl group; Or a R ₃ —Y—X— group, R ₃ is an organic group; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms); Production method. 11. Formula (a) (Wherein Z is oxygen or sulfur element; A is hydrogen or alkali metal), and (b) Zn, Al, Ti, Cu, Mg, Mn, Co, Sn, Ni An oxide, a hydroxide, an inorganic acid salt or an organic metal salt having 1 to 10 carbon atoms, of a metal having a valence of 2 or more, and (c) a polymerizable ethylene bond, A compound having at least one sulfonic acid group, phosphoric acid group, or an alkali metal salt thereof (provided that Z
Is a polymerizable monomer obtained by the reaction with the above) or a copolymerizable monomer which is obtained by polymerizing the monomer and another copolymerizable monomer in the molecule. (In the formula, M is a metal atom having a valence of 2 or more selected from Zn, Al, Ti, Cu, Mg, Mn, Co, Sn, and Ni; 1 is an integer of 2 to 4, and m and n are 0 or 1 respectively. Integer above, where 1 + m + n is metal M
Is equal to the valence of; Y is However, Z is oxygen or a sulfur element; R ₁ is a hydroxyl group; Or a R ₃ —Y—X— group, R ₃ is an organic group; R ₂ is oxygen or a hydrocarbon residue having 1 to 10 carbon atoms); Production method.