JPS62121773A - Antifouling coating - Google Patents

Abstract

PURPOSE:To obtain an antifouling coating which is nontoxic and has a antifouling function, by incorporating a specified phosphorus nitride compound therein. CONSTITUTION:This antifouling coating is composed mainly of a halogenated phosphorus nitride compound of formula I and a coating resin. In formula I, n1 is an integer of 3 or more, at least part of three or more R1's and R2's are each a halogen atom as the essential component, and the remaining R1's and R2's are each -OR3, a group of formula II or -NH-(CH2)n2-COOR3 and may be the same as or different from each other; R3 is CmH2m+1; n2 is an integer of 1-5; m is an integer of 1-20. The amount of the halogenated phosphorus nitride compound to be incorporated is preferably 5-300pts.wt. based on 100pts. wt. coating resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to underwater structures such as ships, marine tanks, buoys, waterway headrace pipes for thermal power plants, coastal industrial seawater equipment, and underwater substrates such as fishing nets such as aquaculture nets and fixed nets. This invention relates to a new antifouling paint that is nontoxic and has long-term antifouling performance.

Various kinds of plants and animals live in water (including seawater), such as fujibo, oysters, sea squirts, sea breams, celluloids, sea lettuce, and green laver. It is a well-known fact that For example, if it adheres to the bottom of a ship, it increases resistance to the water and increases operational fuel consumption, and fishing nets cause various damage such as a decrease in aquaculture productivity.

Conventionally, in order to prevent these damages, organic tin compounds,
It was painted with an antifouling paint containing toxic antifouling agents such as cuprous oxide. The antifouling mechanism of the paint kills the larvae of the aquatic animals and plants by constantly eluting the toxic antifouling agent from the paint film into the water. however,
Since the antifouling agent in this antifouling paint is toxic, it is unfavorable in terms of safety and health during manufacturing and painting of the paint, and furthermore, there is a risk of contaminating the ocean and marine resources by leaching into water.

Therefore, in recent years, research and development has been conducted on so-called non-toxic antifouling paints that do not use toxic antifouling agents.

However, the non-toxic antifouling paints that have been proposed so far include silicone rubber, silicone oil, Teflon resin,
The main ingredient is paraffin wax, etc., or it has been added to it. All of these make the surface energy of the coating film water-repellent and reduce the adhesion of adhesive proteins secreted from the body when attached to aquatic organisms as much as possible. It is a smaller version. However, as a result of studying these non-toxic anti-fouling paints, we found that their anti-fouling properties are not sufficient and are significantly inferior to paints containing the above-mentioned toxic anti-fouling agents, and although it varies depending on the area of water, the anti-fouling properties deteriorate after several months after being submerged in water. Many aquatic organisms were observed adhering to the surface, making it unsatisfactory for practical use.

In view of this situation, the inventors of the present invention conducted intensive research to develop an antifouling paint that is non-toxic and has excellent long-term antifouling properties. The inventors have found that the object can be achieved and have completed the present invention.

That is, the present invention provides a halogenated phosphorus nitride compound represented by the general formula, in which n- is an integer of 3 or more, and at least one part of each of at least three R's and R2 is A halogen element is an essential component, and the remaining R1 and R2 are 10
R3, -0CR3, or 1] -Nll-(CIlz) ng COOR3T: Atte, may be the same or different, where R3 is Cm H2
The present invention relates to an antifouling paint containing the halogenated nitride compound and a paint resin as main components, where a+I+R2 is an integer of 1 to 5, and m is an integer of 1 to 2o.

The feature of the antifouling paint of the present invention is that in order to exhibit the antifouling function, that is, the function of preventing aquatic organisms from adhering to the surface of the paint film in water, the cyclic matrix represented by the above general formula is a chain nitride. A phosphorus compound (hereinafter sometimes abbreviated as an rN-P compound) is contained in a paint.

Although the antifouling function of the coating film formed by the antifouling paint has not been fully elucidated, it is speculated as follows.

(i) The N-P compound in the Sfi coating is hydrolyzed in water and mainly contains ammonia, phosphoric acid, halogen molecules,
It decomposes into alcohol and is gradually exposed to water. Therefore, even if larvae of aquatic organisms try to attach to such a coating surface in water, they will not easily attach because they are constantly being eluted by hydrolysis.

(ii) Since this hydrolyzate is a low molecular weight compound, the coating surface becomes smoother as the immersion period becomes longer, making it difficult for aquatic organisms to adhere to it.

(iii) Furthermore, regarding the concentration distribution of hydrolysates eluted from the surface of the paint film, the concentration is highest near the paint film, and in particular, ammonia, phosphoric acid, halogen molecules, etc. are nutrients for aquatic organisms. However, its concentration is too high near the surface of the paint film, making it difficult to grow. Of course, these are useful as a nutrient source when dispersed and diluted in water.

In addition, the N-P compound and its hydrolyzate used in the present invention are non-toxic and do not kill aquatic organisms at all, but rather reinforce the nutrient source.

Next, the antifouling paint of the present invention will be explained in detail.

The antifouling paint of the present invention mainly contains the N-P compound represented by the above general formula and a paint resin.

P-N compound: A cyclic or chain compound represented by the above general formula, which can prevent aquatic organisms from attaching to it by hydrolyzing the compound.

Hydrolysis of the compound in water is considered to be carried out as follows, for example when R1 is a halogen element. In the hydrolysis formula below, X is an Arogen element.

＋

In the N-P compound represented by the above general formula, the halogen element for R1 is an element selected from fluorine, chlorine, bromine, and iodine, and among these, chlorine, bromine, and iodine are particularly preferable, and furthermore, 101h Alternatively, -0CRi is preferable, and a value of 1 to 10 for Ham in R1 is suitable. Further, nl is an integer of 3 or more, particularly preferably in the range of 3 to 10,000. In particular, in the present invention, it is essential that the N-P compound contains the /S rogane element, and its content is 1% by weight or more, preferably within the range of 5 to 60% by weight. It is. Specifically, alkoxy derivatives such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, 5ec-butoxy, pentoxy and octoxy of chlorine-containing phosphorus nitride,
Cyclic compounds such as chlorine-containing phosphorus chloride nitride phenoxy, chlorine-containing phosphorus chloride nitride benzyl alcohol, chlorine-containing phosphorus chloride nitride glycine ethyl ester, chlorine-containing phosphorus chloride nitride acetoxy and chlorine-containing phosphorus chloride nitride formate, acetate, and propionate; Examples include chain compounds such as chlorine-containing polychlorinated nitride phosphorous phenoxy.

Resin for paint: A resin that is mixed with the N-P compound to fix the compound in the paint film, and is a resin that forms a paint film with excellent water resistance.

Specifically, the formed coating film can be classified into water-soluble resins that gradually dissolve into water and insoluble resins that hardly or not dissolve at all. First, water-soluble resins include carboxyl group-containing resins (acid value of 10 or more), polyamide resins (amine value of 50 or more), etc. Carboxyl group-containing resins include rosin, acrylic resins, vinyl resins, alkyd resins, Examples include polyester resins, oil varnishes, maleated diene resins, etc. Polyamide resins include reaction products of aliphatic polyamines, aromatic polyamines, and polycarboxylic acids. Additionally, cellulose and its derivatives, such as hydroxypropylcellulose and hydroxyethylcellulose propionate, can also be used as water-soluble resins. All of these water-soluble resins have an elution rate of 1500 μg/c/day or more into water, and
000 μg/cII/day or less.

On the other hand, water-insoluble resins are resins whose rate of elution into water is lower than the above, such as natural resins such as shellac and copal, acrylic resins, alkyd resins, epoxy resins, vinyl resins, diene resins, and olefin resins. resin,
Examples include phenolic resins, petroleum resins, rubber resins, cellulose derivatives such as cellulose propionate and cellulose acetate butyrate.

In the present invention, the composition ratio of the above-mentioned N-P compound and paint resin can be arbitrarily selected depending on the purpose of use of the antifouling paint, the water area of the underwater substrate, etc., and is not limited, but usually N-
The amount of the P compound to be blended may be as small as possible in a system with a water-soluble resin, but it is preferable to blend as much as possible in a system with a water-insoluble resin. This is because in the former system, the water-soluble resin gradually dissolves into the water together with the N-P compound, so the N-P compound' is constantly exposed to the eroded painted surface and exerts its antifouling properties. On the other hand, in the latter case, the N-P compound dissolves into water, but the water-insoluble resin remains as a coating film, so in order to maintain antifouling properties for a long time, a large amount of the N-P compound is impregnated into the coating film. It is preferable. Specifically, the blending amount of the N-P compound is 5 to 300% in a system using a water-soluble resin, based on the total amount with the paint resin.
4% by weight, preferably 10 to 200% by weight, and in systems using water-insoluble resins, 5 to 300% by weight, especially 30 to 20% by weight.
It is preferably within the range of 0% by weight. In order to maintain antifouling properties for a long period of time, it is preferable to use a water-insoluble resin containing 30 to 200% by weight of an N-P compound.

The antifouling paint of the present invention has both of the above components as main components, and these two components are usually dissolved or dispersed in an organic solvent.
It is desirable to make it easy to handle during painting work, etc.

Organic solvents generally include, for example, benzene, toluene,
Aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and ethylene glycol monoethyl acetate ether, and alcohols such as methanol, ethanol and isopropyl alcohol are advantageously used.

The antifouling paint of the present invention can be applied by conventional methods such as brush painting, spray painting, roller painting, etc., and the coating film thickness is preferably in the range of 10 to 300 μm based on the dry paint film. The antifouling properties of the underwater substrate coated in this way are comparable to those containing conventional toxic antifouling agents, and it also has the technical effect of being nontoxic.

Next, Examples and Comparative Examples regarding the antifouling paint of the present invention will be described.

Examples 1 to 10 Antifouling paints having the compositions and blending ratios (parts by weight) shown in Table 1.

Comparative example 1 Cellulose propionate solution used in Example 1.

Comparative example 2 A paint made by mixing 10% by weight of cuprous oxide with vinyl chloride resin.

Comparative example 3 Moisture-curing silicone resin paint.

In Table 1, (Nel) Cellulose propionate solution: 25 weight of cellulose propionate (manufactured by Daicel) with a mixed solvent consisting of toluene/methyl ethyl ketone/isopropanol = 1/1/1 (weight ratio) Dissolved in % content.

(Book 2) Cellulose acetate phylate solution fez
: 25% by weight dissolved in the mixed solvent of (*1).

(*3) Acrylic resin solution: A copolymer consisting of methyl methacrylate/2-hydroxyethyl methacrylate = 8/2 (weight ratio) was mixed with a mixed solvent consisting of toluene/isopropanol = 1/1 (weight ratio) at 30% Dissolved in heavy weight content.

(Book 4) Rosin: Chinese gum rosin (Zenni Shoji).

(Rate 5) (A): A mixture of 25 parts by weight of chloronitride phosphorus propoxy having a chlorine content of 25% by weight and 50 parts by weight of isopropanol.

(B): A mixture of 25 parts by weight of phosphorus chloronitride propoxy and 50 parts by weight of isopropanol having a chlorine content of 10% by weight.

(C): A mixture of 25 parts by weight of chlorinated phosphorus butoxy and 50 parts by weight of butanol with a chlorine content of 5% by weight.

(D): A mixture of 25 parts by weight of octylphosphorus chloride nitride and 50 parts by weight of butanol with a chlorine content of 15% by weight.

(E): A mixture of 25 parts by weight of chloronitride phosphorus acetate with a chlorine content of 15% by weight and 50 parts by weight of butanol.

Performance test results The paints shown in the above Examples and Comparative Examples were applied to a mild steel plate that had been previously coated with anti-rust paint (film thickness 100μ) to a thickness of 150 to 200μ based on the dry coating. The test coated plates obtained by drying for 10 days at room temperature were immersed in the sea off the coast of Orito, Shimizu Port, Shizuoka Prefecture for 6 months, and the condition of the coated surfaces was observed, and the results are also shown in Table 1. In the shallow sea test results in the same table, all numbers shown as fractions are the area percentage of aquatic organisms attached to the painted surface, the numerator is Fujibbo and the denominator is Aonori.

Procedural amendment January 2, 1939? Michibe Uga, Commissioner of the Japanese Patent Office 1, Indication of the case, Patent Application No. 258459 of 1985 2, Name of the invention, antifouling paint 3, Person making the amendment Relationship to the case Patent applicant address Kanzaki-cho, Amagasaki City, Hyogo Prefecture 33 No. 1 Name (140) Kansai Paint Co., Ltd. Representative Yama 1
) Group 34, Agent 107 Address: 312 Kyodo Building Akasaka, 4-3-1 Akasaka, Minato-ku, Tokyo Telephone: 586-86706 Column 7 for detailed explanation of the invention in the specification to be amended, Details of the contents of the amendment The detailed explanation column of the book has been corrected as follows.

(1) Page 2 of the specification, lines 19-20: "...larvae..." is corrected to "...larvae, etc...."

(2) Page 5, lines 12-13 of the specification = "Gradually exposed" is corrected to "gradually eluted."

(3) Page 5, line 14 of the specification: "Shiyou" is corrected to "Syo".

(4) Page 6, line 10 of the specification: "Reinforcement" is corrected to "supply."

(5) Specification No. 11, handwritten lines 1 to 8: “Resin for paint.
... is preferable. ” to 100 parts by weight of paint resin, in systems using water-soluble resins, 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and in systems using water-insoluble resins, 5 to 300 parts by weight, In particular, it is preferably in the range of 30 to 200 parts by weight.In order to maintain antifouling properties for a long period of time, it is preferable to use a water-insoluble resin containing 30 to 200 parts by weight of the N-P compound.''

(6) Line 10 of the 12th line of the specification: "(parts by weight)" is corrected to "(parts by weight of solid content)".

Procedural amendment dated 13th lθ, 1985, Commissioner of the Patent Office, Black 1) Mr. Yu Akira1, Indication of the case, 1985 Patent Application No. 2584592, Name of the invention, antifouling paint3, Person making the amendment, Relationship to the case Patent applicant address: 33-1 Kanzaki-cho, Amagasaki-shi, Hyogo Name (140) Kansai Paint Co., Ltd. Representative: Yama
1) Motosan 34, Agent Postal code 107 Address Akasaka 4-3-1 Kyodo Building Akasaka 3, Minato-ku, Tokyo
Telephone No. 12, 586-86706, Subject of Amendment 7, Detailed Description of the Invention column in the Statement of Contents of Amendment is corrected as follows.

(5th line from the bottom of No. 7 of Specification No. 11: "Regarding R1, the halogen element is..." is corrected to "The halogen element of rR+ or R2 is...")

(2) Lines 3 to 1 from directly below No. 7 of the specification = “
Furthermore, ORj...” is changed to “Furthermore, R1 and R2
is corrected to "-OR3...".

(3) Page 14, line 9 of the specification = “Performance test results”
($6) Performance test results”.

(4) Page 15 of the specification, bottom column of the first table: "Shallow sea test results" is corrected to "Shallow sea test results (16) J.

Claims (1)

[Claims] A halogenated phosphorus nitride compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, in which n_1 is an integer of 3 or more, each of which is at least 3
At least a part of R_1 and R_2 is a halogen element as an essential component, and the remaining R_1 and R
_2 is -OR_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, or -NH-(CH_2)n_2-COOR_3, which may be the same or different, where R_3 is C_
mH_2_m_+_1, n_2 is an integer from 1 to 5, m is 1
An antifouling paint comprising as main components the halogenated phosphorus nitride compound, which is an integer of 20 to 20, and a paint resin.