JPS59189175A - Underwater antifouling film former - Google Patents

Abstract

PURPOSE:To provide an underwater antifouling film former having excellent storage stability and capable of forming a coating film which has strong adhesion and retains its antifouling effect over a long period, prepared by using a specified n-vinyl amide compd. as vehicle. CONSTITUTION:Used as vehicle is a copolymer obtained by copolymerization of 10-70pts.wt. N-vinyl amide compd. of the formula (where R<1> is H, 1-8C alkyl, cycloalkyl, aryl, hydroxyalkyl or alkoxyalkyl; R<2> is 1-12C alkyl or aryl) and 30-90pts.wt. other monomers (e.g. methyl acrylate or vinyl chloride). The underwater antifouling film former is obtained by adding a triphenyltin compd. (e.g. triphenyltin hydroxide) (copper suboxide may be used together) to a vehicle consisting wholly or partly of the above copolymer.

Description

[Detailed description of the invention] The present invention relates to an underwater antifouling film forming agent.

Green algae, brown algae, diatoms, sea lettuce, etc., as well as snails, serpura, etc., can be found on the bottoms of ships, fishing nets, and other underwater objects.
Contaminant organisms such as sea squirts, sea squirts, and bryozoans are attached to them, causing various types of damage. Namely.

When these contaminants adhere to the bottom of a ship, the frictional resistance between the ship's hull and seawater increases, reducing the ship's speed and reducing fuel consumption ('11).
Increase costs. In addition, when contaminated organisms adhere to fishing nets, they obstruct the flow of seawater, resulting in poor growth of fish due to blockage of the first mesh.

Therefore, the surfaces of these objects are treated with antifouling agents.

A method has been adopted in which an antifouling coating film is formed on the surface to prevent the attachment and growth of contaminant organisms. Antifouling agents usually consist of a vehicle, an antifouling component, and other additives. As the antifouling component, triphenyltin compounds are used because of their ambiguous antifouling properties, and as vehicles, chlorinated rubber and vinyl chloride resin have traditionally been used. , vinyl chloride/vinyl acetate copolymer resins, etc. have been widely used.

However, these vehicles lack compatibility with the triphenyltin compound, and the triphenyltin compound crystallizes or bleeds onto the surface of the dry/ri coating, making it difficult to obtain a good antifouling coating. These vehicles have a significantly higher initial tin bathing rate.

It has drawbacks such as the fact that it decreases drastically with oral use and falls below the antifouling limit value, making it impossible to provide long-term antifouling performance.

Therefore, even if you try to adjust the elution rate of tin by adding water-soluble rosin (pine resin) to a part of the vehicle, the rosin will elute along with the tin, making it impossible to prevent the coating from occurring.40] (Skeleton)
This increases the frictional resistance with seawater. The triphenyltin compound found in moss reacts with rosin during storage of antifouling paint, making it insolubilized and unstable due to the formation of chloride, resulting in a decrease in susceptibility to seawater and a significant change in paint viscosity, reducing the antifouling effect. accompanied by a decrease in

Furthermore, in antifouling paints that require long-term antifouling properties, 1F oxidized steel is used in combination as an antifouling component, but the triphenyltin compound also destabilizes this coating.

It causes kelization and significant viscosity reduction during storage.

Therefore, in the case of a system for oral/inhalation use, a two-component antifouling agent is emitted with uF1, but this poses problems in manufacturing and use, and is not a fundamental solution.

The inventors have conducted research from these viewpoints.

By using a specific N-vinylamide compound copolymer in part or all of the vinyl, the antifouling paint 2 was made storage stable and an excellent antifouling coating film was successfully formed.

That is, the present invention is directed to forming an antifouling coating film from a vehicle, an antifouling component, and other additives.

(a) Part or all of the vehicle has the general formula (I) 1 1 (wherein R] is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
7 chloroalkyl group, aryl group, hydroquinoalkyl group or alkokinoalkyl g, R2 is 2≠none
N-vinylamide compound monomers 10 to 7 represented by (representing an alkyl group or aryl group having 1 to 12 carbon atoms)
(b) a copolymer obtained by copolymerizing 30 to 90 parts by weight of 0 parts by weight and 30 to 90 parts by weight of one or more other monopolymerizable unsaturated compounds; This is an underwater antifouling coating forming agent characterized by using one or more phenyltin compounds or at the same time cuprous oxide.

Examples of the N-vinylamide compound monomer represented by the above general formula [1] include 6, for example, N-vinylamide, N-
Vinyl N-methylacetamide', N-vinyl N-ethylacetamide, N-donyl N-propylacetamide, N-vinyl N-butylacetamide, N-vinyl N-
Cyclohexylacetamide, N-vinyl N-phenylacetamide, N,-vinyl N-octylacetamide M
, N-vinyl N-hydroxymethylacetami)', N
-Hiniviny hydroxyethylacetamide + N-vinyl N-methoxy, /ethylacetamide, N-vinyl N-
Ethotine ethyl acetamide, N-vinyl N-inobuwapoquin ethyl acetamide (package) N-vinyl propionamide, N-vinyl N-methylpropionamide, N-vinyl N-ethylpropio/amide 1 packet N-vinyl N-human 'oxyethylpropionamide, N-vinyl N-methylbutyramide, N-vinyl N-methylvaleramide, and the like.

Other polymerizable unsaturated monomers to be copolymerized with these N-vinylamide compounds include acrylic compounds and vinyl compounds having functional groups.

Examples include vinyl hydrocarbons and organic tin salts of polymerizable unsaturated carboxylic acids.

Examples of acrylic compounds include methyl acrylate,
Acrylic acid esters such as ethyl, propyl, isopropyl, butyl, amyl, hequinyl, dotenyl, /chlorohexyl, phenyl, he7yl, terahydrofurfuryl ester; methacrylic order methyl, ethyl, butyl, hequinol , octyl, lauryl esters, and other methacrylic acid esters.

Examples of vinyl compounds with functional groups include vinyl chloride, halogenated compounds such as vinylic acid chloride, acrylonitriles such as acrylonitrile and methacrylonitrile, methyl vinyl ether, ethylhinino V needle, β-chloroethyl vinyl ether, and butyl. Vinyl ether, octyl vinyl ether, vinyl ethers of phenyl vinyl ether, methyl vinyl sulfide.

Vinyl thionides such as divinyl sulfide and butyl vinyl sulfide, vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone, and acroleinato;
Examples include vinyl esters such as vinyl formate, vinyl acetate, and vinyl propionate.

Examples of vinyl hydrocarbons include ethylene.

Olefins such as propylene, 1-buteno, cyclohexene, α-pinene: Stire 770! Examples include styrenes such as -methylstyrene, 0-methylstyrene, and p-methylstyrene.

Polymerization IJ, (as an organic tin salt of unsaturated carboxylic acid 2, an example is [-ribropyltin methacrylate 1-.

Examples include tributyltin methacrylate, triphenyltin methacrylate, and l-liptyltin acrylate.

These other polymerizable unsaturated compound monomers are 1 or 2
Can be used in more than one species.

Used in part or all of the vehicle in the present invention 1-,
The N-vinylamide compound copolymer is usually produced as follows. That is, one or two N-vinylamide compound monomers represented by the above general formula j:
Organic peroxide, azo compound, persulfate, etc. in a mixture of 10 to 70 parts by weight of 10 to 70 parts by weight of one or more other polymerizable unsaturated compound monomers and 30 to 90 parts by weight of one or more other polymerizable unsaturated compound monomers. It is prepared by conventional solution, suspension or emulsion polymerization methods by adding a radical polymerization catalyst.

A conventionally known vehicle is pine resin (rosin).

Drying oils, oil vehicles such as terpenes, chlorinated rubber resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, and the like are used. In the present invention, these known vehicles are often required.

It can be used as part of the vehicle if desired.

Examples of triphenyltin compounds used as antifouling components in the present invention include triphenyltin hydroxite, bis(triphenyltin) oxide, triphenyltin chloride, triphenyltin acetate, triphenyltin fluoride, and bis(triphenyltin) oxide. Examples include triphenyltin dibromsuccinate, l.liphenyltin dimethyldithiocarbamate, and these can be used alone or in combination of two or more. In the present invention, cuprous oxide is used in combination with a triphenyltin compound, especially when long-term stain resistance is required.

If necessary as an antifouling component, other copper compounds such as cuprous chloride, copper rhodan, copper naphthenate, other organic tin compounds such as bis(l-liptyltin) oxide, tributyltin fluoride l-', For l-linklohequinyltin hytrooxite and other antifouling toxic substances, dimethyldithiocarbame-1.zinc, tetrachloroinphthalonitrile, thiuram compounds, etc. can be added.

Other additives optionally used in the practice of this invention include titanium oxide, zinc white, and Bengara.

Pigments for buttons, dyes such as 7-anine green, polyazolet, etc., additives such as bentonite l-, talc, etc. Drying agents such as cobalt phthenate and manganese naphthenate, other solvents, modifiers, etc. Examples of solvents include hydrocarbons such as hensen, toluene, quinolene, 7-chlorohexano, hexane, heptano, and octano; alcohols such as methyl, ethyl, propyl, butyl, and amyl alcohol; dimethyl ethyl ketone, methyl isophyl ketone; )・Ketones such as ethyl pertoate.

esters such as butyl; petroleum hydrocarbons such as ligroin 2 petroleum benzene; mineral spirits;
Examples include celonorb and grime.

The underwater antifouling film-forming agent of the present invention contains ~70 parts by weight of the N-vinylamine compound monomer represented by the above general formula [1] in part or all of the vehicle and other polymerized vine unsaturated compounds. f
A copolymer obtained by copolymerizing 30 to 90 parts by weight of one or more types of compound monomers, a triphenyltin compound or triphenyltin compound and cuprous oxide as an antifouling component, and other additives. It consists of

When the N-vinylamide compound monomer unit in the copolymer is 100 parts by weight or less, the elution rate of tin from the antifouling coating surface to the seawater is abnormally high at the initial stage and the attenuation is significant, and the dip coating film A cavity can be seen. On the other hand, if the monomer unit is more than 70% by weight, the seawater resistance of the antifouling coating will deteriorate, the coating will swell, become tarnished, or peel off, or become unnecessary.
The second tin is eluted. Therefore, if the monomer ratio is outside the range of the present invention, an antifouling coating film that is effective for a long period of time cannot be formed.

The N-vinylamide compound copolymer used in the present invention has excellent compatibility with the triphenyltin compound, so it can contain a high concentration of the triphenyltin compound, making it transparent or translucent. It is possible to form a continuous coating film. Contains both of these. Addition of rosin or cuprous oxide to the antifouling coating (2) does not cause the coating to kelp or decrease in viscosity during long-term storage, but is stable and can be used as a liquid-type coating.

The produced underwater antifouling film-forming agent of the present invention is treated by methods commonly applied to substrates damaged by contaminating organisms, such as coating, dipping, and spraying.

When a substrate is treated with the underwater antifouling film-forming agent of the present invention, the adhesion and durability of the coating film are better than when the substrate is treated with an antifouling film-forming agent produced from a conventional vehicle. The elution of the antifouling component into water is appropriately controlled, and the antifouling effect can be maintained over a long period of time.

Next, the present invention will be explained with reference to production examples, working examples, and test examples. Parts indicate parts by weight and 1% indicates parts by weight.

(Production example of copolymer) 130 parts of N-vinyl N-methylacetamide, 45 parts of methyl nucleate and octyl acrylate were placed in a reaction vessel.
Add 1.25 parts and melt to 00 parts.

Then add 0.6 @
Copolymerize for 6 hours at 5-so'c, and further ] ] 0
The temperature was raised to 'C, heated for 1 hour, and then cooled to obtain a 50% Gilun solution of a pale yellow and transparent copolymer with a viscosity of 12 voids (25°C) (this will be referred to as copolymer solution (1)). Ta.

(Copolymer production examples 2 to 5) N-vinyl N-methyl ado not shown in Table 1 below.

1.00 parts of a monomer mixture consisting of each part of methyltutaacrylate and octyl acrylate was dissolved in 1.00 parts of quince, and copolymerized under the same conditions as in Production Example 1 to obtain a viscosity of 2.
A 50% xylene solution of a pale yellow to yellow transparent copolymer with ~30 voids (25°C) (this was mixed into a copolymer solution (old ~ (
V ) was obtained.

Table 1 (Copolymer Production Examples 6 to 9) 100 parts of a mixture consisting of each part of the monomers shown in Table 2 below was placed in a reaction vessel and dissolved in 100 parts of Kinolev. Next, add 06 parts of asohisuibuteronitrile, replace the inside of the container with nitrogen, stir in a nitrogen stream, and add 75 to 80 parts.
Copolymerize for 5 hours at 100°C, then raise the temperature to 05°C, heat at IB1 for 1 hour, cool, and reduce the viscosity to 3-2C voids (
A 50% xylene solution of a pale yellow to yellow transparent copolymer (referred to as copolymerization 1 solutions (■) to (IX)) was obtained at a temperature of 25°C.

Table 2 (Manufacturing Examples A-D of Comparative Copolymers) Polymerization was carried out under the following conditions, and the viscosity was 2 to 30 poise (25°
50 solutions of transparent copolymers having C) (referred to as copolymer solutions (A) to (D)) were obtained.

Table 3 (Note) Polymerization conditions are as follows.

Production example A-B: Dissolved in 100 parts of xylene and added 06 parts of benzoyl peroxide.
1 hour at 120°C.

Production example C-D: Dissolved in 100 parts of isobutyl alcohol, added 06 parts of azobisinobutyronitrile, 75-8
6 hours at 0°C, 1 hour at 105°C.

Examples 1 to 18 and Comparative Examples 1 to 8 30 parts of the following copolymer solution, 12 parts of triphenyltin compound
1 part and 10 parts of xylene were uniformly dissolved to prepare an antifouling paint.

Example 1) Triphenyltin chloride'/
2 (I) Triphenyltin hydroxide〃30J) l-Riphenyltin chloride〃・
1 (formerly triphenyltin) itrooxide〃5
(nD triphenyltin chloride 6 (IJ
I) l-Riphenyltin hydroxide [・〃7
(■) l-Riphenyltin chloride〃8 (■
) l-Riphenyltin hydroxide〃9(■)
Triphenyltin chloride〃10(v) Triphenyltin/・itrooxide〃1
1 (■) Triphenyltin chloride 12 (U
l-Riphenyltin hydroxide〃13(■l)triphenyltin chloride〃1.4. (Vl[)
Triphenyltin hydromangiside // 15
()・IiD l-rephenyltin chloride //
16 (1・1ll) Triphenyltin hydroxide〃17 (IX) Triphenyltin chloride” 18 (IX) l-!J Phenyltin・
・Itroxide comparative example 1 (A,) l'
Life=tin chloride〃2(A) Triphenyltin hydroxide〃3(B) Triphenyltin chloride///1. (B) l-liphenyltin-
Hydroxite〃5 (C) L-Riphenyltin Chloride〃6 (c) Triphenyltin/-Itrooxite” 7 (D) L-Riphenyltin Chloride〃8 (1) Triphenyltin-Idrooxide Tip Example 19-36 and Comparative Examples 9-18 Vehicle components in Tables 4.4 to 4-2 below.

Each part of the antifouling ingredients and other additives were used in a ball mill to make an antifouling paint.

Table 4-2 (Note) VC/VAc in Tables 4-1 and 4-2.

Pll and DBS mean the following:

VC/VAC: Vinyl chloride/vinyl acetate.

Ph: phenyl, DBS: dibromosaxonate*
Mark: CR-20 made by Asahi Denka Co., Ltd. **Mark: Vinylai 1-B-5507 (manufactured by Union Carbide Co., Ltd.) Test Examples] Each antifouling coating obtained in Examples 1 to 18 and Comparative Examples 1 to 8 was applied to the surface of a vinyl chloride resin board (150 x 70 m +
A coating film was formed by drying in a C oven for 8 hours. For each test plate obtained, the coating film condition, seawater resistance, and tin elution rate were determined using the following methods.

An antifouling test was conducted.

The results are shown in Table 5.

(Dried coating state) The surface coating of each test plate obtained above was observed with the naked eye, and the transparency, continuity, and presence or absence of surface crystallization of the coating were examined.

(Seawater resistant 1 cow) Each test plate was immersed in Nrj water for one month, then taken out, and the coating film was observed with the naked eye and under a microscope to check for swelling, flaking, and skeleton.

(Elution rate of tin) After each test plate was immersed in seawater for a predetermined number of days, tin eluted from the test plate was measured by atomic absorption spectrometry.

(Anti-fouling immersion test) Each test plate was placed at a water depth of 5η/m in Owase Bay, Mie Prefecture.
We observed the presence of contaminant organisms.

(Sho) Symbols and numbers in the table (dry coating state) ◎: Transparent i94 continuous coating film ○: Translucent or opaque continuous coating film △: Opaque discontinuous coating film ×: Surface crystallization (antifouling immersion test) O : No attached organisms 1: 〃 20% or less 2: tt 40% or less 3: 〃 60% or less 4: 〃 80% or less 5: 〃 80% or more Test 1 Test Example 2 Examples 19 to 3G and Comparative Examples 9 to 18 Each of the antifouling paints obtained in step 1 was stored in a tin can in an oven at 50°C, and taken out after weeks, one month, and two months to check for changes in the viscosity of the paints.

In addition, each antifouling paint was placed in a separate tin can, and the paint immediately after manufacture and the paint stored at room temperature (25°C) for 2 months and 5 months were treated in exactly the same manner as in Test Example 1, and the paints were placed on a vinyl chloride resin film board. of,
Apply to the surface at a concentration of 1.50/l.

After drying, a coating film was formed. An antifouling test was conducted on each of the test plates obtained in the same manner as in Test Example].

The above results are shown in Table 6.

(Note) Symbols and numbers in the table (Storage stability) A. No change in initial viscosity B, Slight change C゛　　　　　There is a significant change D: Kelization (Anti-fouling immersion test) 0 to 5: Same meaning as listed in Table 5 Patent applicant Nitto Kasei Co., Ltd. Agent Patent Attorney Tetsuya Matsu -483-

Claims (1)

[Claims] 1. In forming an antifouling coating film from a vehicle, an antifouling component, and other additives. (a) Part or all of the vehicle has the general formula CI)H (where R1ft hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, an aryl group, a hydroxyalkyl group, or an alkoxy7alkyl group). + R2 is water, half and four tan;
(represents an alkyl group or aryl group having 1 to 12 carbon atoms)
N-vinylamide compound monomer represented by 10 to 70
A copolymer obtained by copolymerizing 30 to 90 parts by weight and 30 to 90 parts by weight of one or more other polymerizable unsaturated polymers; An underwater antifouling film forming agent characterized by using one or more phenyltin compounds, or at the same time cuprous oxide.