JP3261220B2 - Underwater antifouling paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is excellent in storage stability and can maintain stable antifouling performance for a long period of time.
It relates to an underwater antifouling paint composition.

[0002]

2. Description of the Related Art An antifouling paint using an organotin copolymer, in which a coating film gradually dissolves in seawater, has excellent antifouling performance for preventing the adhesion of marine organisms to the surface of ships and the like. However, their use has been restricted in recent years due to the problem of marine pollution.

In order to prevent the problem of marine pollution, an antifouling paint using an organic silicon-containing polymer in which a seawater-soluble organic silicon ester is introduced into a side chain is disclosed in US Pat.
It is disclosed in the specification of 3,055. The coating film formed from this antifouling paint is one in which the surface of the coating film is gradually dissolved in seawater due to hydrolysis, thereby maintaining the antifouling effect for a long period of time and reducing fuel consumption of ships and the like.

[0004]

However, when the above-mentioned organosilicon-containing polymer is mixed with copper or a copper compound to form an antifouling paint in order to improve the antifouling performance, the paint is gradually coated during the storage period. However, if the viscosity of the product increases, it becomes gelled when it is remarkable, making it impossible to paint. This impairs the value as a product, and even if it can be painted, the antifouling performance becomes insufficient.

[0005] The present invention provides an underwater proofing system which can maintain stable antifouling performance for a long period of time and has improved storage stability.
It is intended to provide a soil paint composition.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by adding a specific organic silicon compound to an organic silicon-containing polymer, copper or a copper compound has been obtained. The inventors have found that excellent storage stability can be obtained even when coexisted, and that the antifouling performance can be maintained for a long period of time, and the present invention has been completed.

That is, the present invention provides A) a compound represented by the following formula: (In the formula, R ^{1 to} R ³ are each a group selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group and an aralkyl group. an organosilicon-containing polymer having a tri organosilicon ester group represented by mediation in different groups may be), B) and a copper or a copper compound as a major component, tables
In an underwater antifouling paint composition containing no surface lubricant , C)
The following formula: (Wherein, R ^{4 to} R ⁶ each represent a hydrogen atom,
8 alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, cycloalkoxy groups, aryl groups
It is a group selected from a roxy group and an arylalkoxy group, and may be the same or different groups. R ⁷ is an alkyl group, a cycloalkyl group, ants having 1 to 18 carbon atoms - a group or aralkyl group. n
Is an integer of 1 to 3. The alkoxy group-containing silicon compound represented by the formula (A)
Water characterized by being included as an essential ingredient other than the ingredients
The present invention relates to a medium antifouling paint composition.

[0008]

The organosilicon-containing polymer of the component A used in the present invention includes an organosilicon-containing monomer having a triorganosilicon ester group represented by the above formula (I) (hereinafter referred to simply as "monomer"). Monomer A) and one or more polymers (hereinafter, referred to as polymer A), and the above-mentioned monomer A and a vinyl monomer copolymerizable therewith (hereinafter, monomer B) That)
One or copolymer of two or more (hereinafter, co polymer A of
B), and if necessary, the above-mentioned polymer A and copolymer AB may be used in combination.

The monomer A, which is a constituent unit of the polymer A or the copolymer AB, is a polymerizable unsaturated monomer in which a monobasic unsaturated acid or a dibasic unsaturated acid and a triorganosilicon-containing compound are ester-bonded. Compound. Examples of the monobasic unsaturated acid include acrylic acid, methacrylic acid, monoalkyl maleate, monoalkyl fumarate and monoalkyl itaconate. Examples of the dibasic unsaturated acid include maleic acid, fumaric acid, itaconic acid and the like.

Specific examples of such a monomer A include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, 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,
Triphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, di-i-propyl-n
-Butylsilyl (meth) acrylate, di-i-propyllaurylsilyl (meth) acrylate, di-i-propylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t- Butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, tri-i-propylsilylmethyl maleate, tri-i-propylsilyl amyl maleate, tri-n-butylsilyl- n-butyl maleate, t-butyl diphenylsilylmethyl maleate
G, t-butyldiphenylsilyl-n-butylmale
And tri-n-butylsilylmethyl itaconate.

The monomer B as a structural unit of the copolymer AB includes methyl (meth) acrylate, ethyl (meth)
Acrylate, n-butyl (meth) acrylate, i-
Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylates such as cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate , Vinyl chloride, vinylidene chloride, (meth) acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl butyrate, veova (manufactured by Ciel), i-butyl vinyl ether, lauryl vinyl ether, Vinyl compounds having a functional group such as N-vinylpyrrolidone; styrene, vinyltoluene, α-
Aromatic vinyl compounds such as methylstyrene; dimethyl maleate, di-n-butyl maleate, dimethyl fumarate,
And dialkyl ester compounds of unsaturated dibasic acids such as di-n-butyl fumarate. The amount of the monomer B to be used may be appropriately determined according to the coating film properties such as the coating film hardness.

The method for synthesizing the polymer A or the copolymer AB is as follows.
Optional, using various radical polymerization catalysts such as organic peroxides and azo compounds, by a known polymerization method such as a solution polymerization method, an emulsion polymerization method, a solid polymerization method, a bulk polymerization method,
Can be synthesized. Of course, these commercially available products may be used. The use amount of the component A composed of the polymer A and / or the copolymer AB is preferably set to a ratio which is usually 5 to 50% by weight based on the total solid content of the coating material.

The copper or copper compound of the component B used in the present invention includes copper powder, copper alloy powder, cuprous oxide, rodan copper, copper phosphide, copper resinate, copper naphthenate, copper hydroxide, thiocyanate Copper oxide, copper carbonate, copper chloride, copper sulfate and the like can be mentioned.
The amount of the B component composed of copper or a copper compound is preferably set to a ratio which is usually 10 to 90% by weight based on the total solid content of the paint.

The alkoxy group-containing silicon compound of the component C used in the present invention, as represented by the above formula (II), has at least one alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group, A compound having an aryloxy group or an alkylaryloxy group, for example,
Tetraethoxysilane, tetrabutoxysilane, tetrakis (2-ethylhexyl) silane, tetrakis (2-
Tetraethoxysilanes such as ethoxybutoxy) silane and tetraphenoxysilane; triethoxysilane, ethyltriethoxysilane, dodecyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxy Trialkoxysilanes such as silane and aminopropyltriethoxysilane; dimethyldiethoxysilane, didodecyldiethoxysilane, γ-chloropropyldiethoxymethylsilane, methylphenyldiethoxysilane, diphenyldiethoxysilane, bis (2- Dialkoxysilanes such as chloroethoxy) dimethylsilane; monoalkoxysilanes such as trimethylethoxysilane, triphenylethoxysilane and benzyldimethylethoxysilane; Chill isopropyl silane,
Trimethyl n-propoxysilane, 1,1,3,3-
Tetramethyl-1,3-diethoxysiloxane, 1,3
-Dimethyl-1,1,3,3-tetraethoxysiloxane, 1,3-diphenyl-1,1,3,3-tetraethoxysiloxane, hexakis (2-ethylbutoxy) disiloxane, methyltris (tris-butylsiloxy) Disiloxanes such as sanyl) silane, 1,1,3,3,5,5-hexamethyldiethoxytrisiloxane, 1,1,3,5,5-pentaethoxy-1,3,5-trimethyltrisiloxane Or trisiloxane. One of these alkoxy group-containing silicon compounds may be used alone, or two or more thereof may be used in combination.

In the present invention, the amount of the alkoxy group-containing silicon compound as the component C is usually 0.1% in the total solid content of the paint.
It is good to set the ratio to 1 to 50% by weight, preferably 1 to 20% by weight. Even if the amount of the alkoxy group-containing silicon compound exceeds 50% by weight, no further effect can be expected.

In the present invention, the method of mixing the alkoxy group-containing silicon compound as the component C is not particularly limited, and a method of adding the compound at the time of synthesizing the polymer, a method of adding the compound at the time of preparing the paint or immediately after the preparation, and the like can be used. It is possible.

The underwater antifouling paint composition of the present invention comprises the above A
-C component as an essential component, and, if necessary, pigments such as zinc oxide, red iron oxide, titanium dioxide, talc; dioctyl phthalate (DOP), tricresyl phosphate (TCP), chlorine Plasticizers such as fluorinated paraffin; resins such as acrylic resin, chlorinated rubber, and rosin; tetrachloroisophthalonitrile, 3,4-dichlorophenyl-1,1
-Organic antifouling agents such as dimethyl urea and 2-mercaptopyridine N-oxide zinc; solvents such as xylene, toluene, butyl acetate and methyl isobutyl ketone; addition of anti-sagging agents and anti-settling agents commonly used in paints It may contain an agent.

[0018]

The underwater antifouling coating composition of the present invention has good mixing and dispersing properties at the time of coating preparation, and has good stability after mixing and dispersing.
In other words, it has excellent storage stability, and is used for the bottom of ships that need to prevent biofouling in the sea, underwater structures such as fish nets and cooling water pipes, and membranes for preventing sludge diffusion in marine engineering works. And an excellent antifouling effect against biofouling of the surface of the object can be maintained for a long period of time.

[0019]

Next, the present invention will be specifically described with reference to Production Examples, Examples and Comparative Examples. Parts and percentages in the examples are on a weight basis. The molecular weight indicates a weight average molecular weight (in terms of polystyrene) determined by GPC.

Production Examples 1 to 6 A 1,000 ml flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with the solvent (1) in accordance with the formulations shown in Tables 1 and 2, After raising the temperature to a predetermined reaction temperature and stirring, a mixed solution of the monomer A, the monomer B, and the polymerization catalyst (1) was dropped into the flask over 2 hours. ) Was added and the reaction was continued at the same temperature for 4 hours. After the reaction, the solvent (2) was added for dilution to obtain six types of pale yellow polymer solutions P1 to P6. In addition, about the polymer solution P6, the alkoxy group-containing silicon compound of the C component was added at the time of preparing the polymer solution. The viscosity and nonvolatile content of the polymer solution were as shown in Tables 1 and 2.

[0021]

[Table 1]

[0022]

[Table 2]

Examples 1 to 10 A polymer solution of component A, a copper compound of component B, a pigment, a plasticizer, a dispersant and an organic antifouling agent were mixed and dispersed in accordance with the formulations shown in Tables 3 to 5. Thereafter, the remaining component including the alkoxy group-containing silicon compound of the component C is further added, and 10 kinds of
An underwater antifouling paint composition (hereinafter simply referred to as a paint composition) was prepared. In the coating composition of Example 10, since the polymer solution P6 used contained the alkoxy group-containing silicon compound of the component C, another alkoxy group-containing silicon compound was not added in this coating preparation step.

[0024]

[Table 3]

[0025]

[Table 4]

[0026]

[Table 5]

Comparative Examples 1 to 4 According to the composition shown in Table 6, a polymer solution of the component A, a copper compound of the component B, a pigment, a plasticizer, a dispersant and an organic antifouling agent were mixed and dispersed, and the remaining components were mixed. Is further added to the composition to obtain four comparative underwater antifouling paint compositions (hereinafter simply referred to as paint compositions).
A) that was prepared.

[0028]

[Table 6]

The above Examples 1 to 10 and Comparative Examples 1 to 4
Each of the coating compositions was subjected to a storage stability test, a coating consumption test and an antifouling performance test in the following manner. These results were as shown in Tables 7 to 9 below.

<Storage Stability Test> Each of the coating compositions was placed in two 200 ml round tin cans, one of which was placed in an oven at 50 ° C. for 2 weeks, and each of the other was stored. One was left in a room at 20 ° C. for 6 months, and the change in viscosity before and after the test was examined.

<Coating film wear test> Each coating composition, which was stored in an oven at 50 ° C for 2 weeks after preparation, was placed on the front surface of a steel plate (100 mm x 100 mm x 1 mm) with a rustproof coating on the back surface. Was spray-coated so as to have a dry film thickness of 200 μm, and dried in a room at a temperature of 20 ° C. for one week to obtain a test piece. However, since the paints of Comparative Examples 1 to 4 were gelled,
After adding and dissolving tetrahydrofuran, it was coated. After fixing the above test piece on the outer surface of a cylindrical drum having a diameter of 50 cm, it was immersed 1 m below the sea surface in Owase Bay, Mie Prefecture, and rotated by a motor so that the peripheral speed of the drum became 16 knots.
The exhausted coating thickness was measured every month for 18 months. Further, the average speed of consumption of the coating film thickness (μm / month) was calculated. In addition, if the average coating film thickness consumption speed is 4 μm / month or more, it correlates with good antifouling performance.

<Antifouling performance test> After the preparation, each coating composition stored in an oven at 50 ° C and stored for 2 weeks was applied on both sides of a hard vinyl chloride plate (200 mm x 100 mm x 2 mm) with a dry film thickness of one side. Spray paint on both sides to 200μm,
The test piece was dried in a room at a temperature of 20 ° C. for one week.
However, since the coating materials of Comparative Examples 1 to 4 were gelled, they were applied after dissolving by adding tetrahydrofuran. This test piece was 1.5 m below sea level for 18 months at Owase Bay, Mie Prefecture.
And the ratio of the area occupied by the living organisms on the coating film of the test piece was measured over time. In addition, as the attached organisms, the case where glue on the surface of the coating film and adhesion of Fujitsubo or Celbra were recognized was indicated as (*).

[0033]

[Table 7]

[0034]

[Table 8]

[0035]

[Table 9]

As is evident from the results of Tables 7 to 9, in each of the coating compositions of Comparative Examples 1 to 4 which did not contain the alkoxy group-containing silicon compound as the component C, the storage stability test and the coating film consumption test were performed. Each of the coating compositions of Examples 1 to 10 of the present invention has excellent storage stability, and the consumption rate of the coating film is effective over a long period of time. Since it is uniform, it can be easily understood that stable antifouling performance can be maintained for a long period of time.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayasu Ito 2-86 Senju, Itami-shi, Hyogo (72) Inventor Masashige Taniguchi 6-23, Kadokoda-cho, Nishinomiya-shi, Hyogo (72) Inventor Shigeo Fukuda Nishinomiya-shi, Hyogo 6-23, Kadokokada-cho (56) References JP-A-3-31373 (JP, A) JP-A-3-31372 (JP, A) JP-A-60-44552 (JP, A) JP-A-58-19361 (JP, A) JP-A-5-25423 (JP, A) JP-A-63-57676 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 133/00-143 / 04 C09D 5/14-5/16

Claims (1)

(57) [Claims] 1. A) In a molecule, the following formula: (In the formula, R ^{1 to} R ³ are each a group selected from an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group and an aralkyl group. an organosilicon-containing polymer having a tri organosilicon ester group represented by mediation in different groups may be), B) and a copper or a copper compound as a major component, tables
In an underwater antifouling paint composition containing no surface lubricant , C)
The following formula: (Wherein, R ^{4 to} R ⁶ each represent a hydrogen atom,
8 groups selected from the group consisting of alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, cycloalkoxy group, aryloxy group and arylalkoxy group Or a different group. R ⁷ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. n is 1 to
It is an integer of 3. The alkoxy group-containing silicon compound represented by the formula (A)
Water characterized by being included as an essential component other than the components
Medium antifouling paint composition.