JPS6028456A - Nonhydrolyzable self-grinding antifouling coating composition - Google Patents

Abstract

PURPOSE:To obtain titled composition capable of preventing ships, etc. from fouling caused by marine organisms sticking to them, by formulating, in specific proportion, three components, i.e., a rosin sparingly soluble in sea-water, inorganic antifouling agent soluble in sea-water, and resin compatible with rosin. CONSTITUTION:The objective composition comprising (A) a rosin sparingly soluble in sea-water (pref. with an acid value >=120, and a melting point >=40 deg.C; e.g., wood rosin), (B) an inorganic antifouling agent virtually dissolvable in sea- water (pref. with a solubility to sea-water between 0.1ppm and 10%; e.g., cuprous oxide, copper thiocyanate), and (C) a resin conpatible with rosin (pref. with a solubility parameter Sp between 7 and 12 and non-three-dimensional crosslinkability) with a volume ratio : (A+B)/C falling between 98/2 and 60/40 and a volume ratio : A/C falling between 95/5 and 50/50.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a non-hydrolyzable, self-polishing antifouling paint that prevents the fouling of marine organisms adhering to ships, fishing nets, marine structures, thermal power plant cooling systems, etc. It is related to.

Organic tin pendant polymers have conventionally been used as self-polishing antifouling paints. This is because the paint film is hydrolyzed in seawater, gradually dissolving in the seawater, disappearing from the paint film surface, and being consumed. In contrast, the present invention is characterized in that the coating film is gradually worn away from the surface of the coating film without such hydrolysis.

Self-polishing antifouling paints constantly expose new surfaces as the surface of the paint film disappears, and the elution of the antifouling agent is controlled over a long period of time, making it possible to maintain the antifouling effect. In addition, the surface roughness of the paint film is reduced by self-polishing, and it also suppresses the increase in surface roughness due to the remaining laminated paint film caused by repainting at each repair dock. The frictional resistance of the hull is reduced, and as a result, a large amount of fuel consumption can be saved during the operation of the ship.

In conventionally used organotin pendant polymers, the trialkyltin ester in the polymer side chain is hydrolyzed in slightly alkaline seawater, creating a carboxyl group in the main chain and becoming a sodium salt, which increases the hydrophilicity of the polymer. It dissolves as the amount increases. Furthermore, although these organotin pendant polymers work as trialkyl brocade antifouling agents released by hydrolysis, their antifouling effects are not necessarily sufficient, and cuprous oxide It is essential to use it in combination with an antifouling agent such as rosin, and it can be said that the role and characteristic of organic tin is rather its self-polishing property due to hydrolysis. By using a resin that is compatible with the resin in an appropriate ratio, the present invention has been achieved by surprisingly easily achieving self-polishing properties.

That is, the present invention provides a combination of a rosin that is slightly soluble in seawater and an inorganic antifouling agent that is substantially soluble in seawater;
Volume ratio of rosin and compatible resin is 98 = 2 to 60
:40, and the volume ratio of the rosin and the resin compatible with the rosin is 95=5 to 50:50, and the coating film formed by these compositions is prepared using a hydrolyzer JS. It has a self-polishing property that allows the coating to gradually wear away in seawater without any damage.

Further, the present invention provides a volume ratio of rosin slightly soluble in seawater, the sum of a resin compatible with rosin, and an inorganic antifouling agent that can be substantially dissolved in seawater in a range of 95:5 to 40. :60 is required. This is because if the volume ratio of the antifouling agent is less than 5 cm, the antifouling paint's effect of inhibiting attached organisms will be almost completely lost, and if it exceeds 60 cm, the continuous film property as a paint The physical properties of the film are poor, cracks and blisters are more likely to occur, and adhesion is also impaired.

The resin that is compatible with rosin has a solubility parameter Sp
is preferably in the range of 7.0 to 120. If an incompatible resin outside this range is used, the resin will separate from the rosin, resulting in poor paint condition and poor storage stability. bad. In addition, in the case of incompatible resins, the formation of the coating film is uneven, so there is no continuous self-polishing effect at all, in some cases no self-polishing at all, and in some cases it disintegrates in a short period of time. , it gets washed away.

The resin compatible with rosin is desirably a resin that does not undergo three-dimensional crosslinking. However, even if the glaze is a two-component system or a multi-component system and is not susceptible to cross-linking, if it is used as a - component, or if a certain glaze's multi-component system is not susceptible to cross-linking reactions, there is no problem in using them. do not have. When a crosslinked resin is used, the self-polishing effect is reduced.

In radical polymerization resins that are compatible with rosin, ~Resin A
It is desirable that the ogP value is 1.40 or more. In particular, radical polymer resins are preferable for producing the non-hydrolyzable self-polishing antifouling paint of the present invention, and the self-polishing effect can be easily increased or decreased (by adjusting the monomer composition and degree of polymerization). .

If LogP is less than 1.40, the compatibility between the resin and rosin is poor, the resins will collect together from the beginning, and the rosin and antifouling agent will not show a sustained release effect after dissolving, leaving a resin residue. It remains. Furthermore, if the AogP value becomes even smaller, phase separation from the rosin occurs, causing paint film failure, causing swelling, blistering, and peeling.

Here, the AogP value used in the present invention refers to the distribution coefficient P of a certain substance between water and an organic solvent. (in this case, water and occunor), which is adapted to @ fat, and each 7-ragment constant #1 in the molecule. The sum of f is Ao
It was calculated assuming that it holds true as gP, and LOgP-
It is denoted by Σf.

When log P is calculated according to Table 1 (written by Y. C. Martin, translated by Toshiyuki Ezaki, ``Quantitative drug design method''), for example, in the case of a homopolymer, the AogP value of the heptamer component is calculated as the AogP value of the polymer. and AogP for copolymers.
The value is calculated as follows.

Aog Pi = togP of component i Table 2 shows the AogP value of the radical polymer using these calculation methods.

Examples of resins that are compatible with these rosins used in the present invention include acrylic resins and styrene resins.

Vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, ethylene vinyl acetate copolymer, urea resin.

Melamine resin, guanamine resin, epoxy resin.

Alkyd resin, polyester resin, styrene butadiene resin, chlorinated rubber, chlorinated polypropylene.

Phenolic resin, urethane resin, polybutadiene.

Boxychlorobentadiene, coumaron-indene resin, xylene resin 9 Petroleum resin, chthonic resin, natural rubber, synthetic rubber, etc. may also be modified or blended for the purpose of improving compatibility with rosin.

The rosin used in the present invention has an acid value of 120 or more,
Rosin having a melting point of 40°C or higher includes gum rosin produced from pine tar, wood rosin extracted from pine roots and stumps, or tall oil rosin separated from tall oil by-product of kraft pulp.

If the acid value of the rosin is less than 120, the solubility of resin acids such as abietic acid in seawater will be poor, and the self-polishing paint of the present invention will not be suitable. , it becomes impossible to maintain sufficient physical properties during coating film formation.

These rosins may be used alone or in combination, and modified rosins such as polymerized rosins, hydrogenated rosins, dibasic acid-modified rosins, and rosin derivatives may also be used.

The inorganic antifouling agent used in the present invention that is substantially soluble in seawater has a solubility in seawater of 0.1 ppm to 1 pm.
It shows a solubility in the range of 0.

Strontium mate, cupric chromate, cupric citrate, cupric ferrocyanate, cupric quinoline.

Copper δ-hydroquinoline, cupric oleate, cupric oxalate, cupric phosphate, cupric tartrate, cupric chloride, cupric iodide, cuprous sulfite, copper naphthenate, etc. There is,
Use 1 m4 or 2 or more of these.

In the antifouling paint composition of the present invention, abietic acid and grooved acid as rosin components are gradually dissolved in seawater1, and an inorganic antifouling agent that is substantially soluble in seawater is ionized and dissolved. By doing this, if the resin that is compatible with rosin near the surface of the coating film that comes into contact with seawater has a composition ratio as shown in the present invention, the cohesive force between molecules will no longer work, and it will easily dissolve in seawater. It is thought that it is liberated and released. However, the higher the volume fraction in the coating film, which is the sum of the rosin that is slightly soluble in seawater and the inorganic antifouling agent that is substantially soluble in seawater, the higher the self-polishing property.

Furthermore, the more uniformly the resin that is compatible with rosin is dispersed and the smaller its cohesive force is, the easier it is to control self-polishing properties.

In the present invention, antifouling agents used in general antifouling paints can be used. For example, organic tin monomers include tributyltin fluoride, tributyltin chloride, tributyltin acetate, tributyltin laurate, tripropyltin chloride, )', triamyltin acetate, and triphenyltin fluoride.

)! j Phenyltin nicotinate, triphenyltin sulfide, bistriphenyltin α, α-dibromosuccinate, triphenyltin chloride, triphenyltin persatate, tricyclohexyltin monochloroacetate, bis(tributyltin) oxide, bis(triphenyltin) oxide.

Bis(tricyclohexyltin) sulfide, bis(tri-2-ethylbutyl) oxide, bis(tri-5
As a triazine compound such as ec-butyltin) oxide, 2-chloro-4,6-bis(ethylamino)-
8-) Riazine, 2-chloro-4-ethylamino-6-
Ituburobylamino-S-) riazine, 2-chloro-4
, 6-bis(isopropylamine)-8-triazine,
2-/l xy4. e-bis(ethylamino)-S-triazine, 2-methylthio-4,6-bis(ethylamino)-8-)lyazine, 2-methylthio-4,6-bis(isopropylamine)-8-)lyazine, 2-Methylthio-4-ethylamino-6-inglobylamino-8
-) riazine and more zinc dimethyl carbamate,
Organic sulfur compounds such as tetramethylthiuram disulfide may also be used.

The antifouling paint composition of the present invention also contains inorganic pigments such as titanium oxide, carbon black, red iron oxide, talc, chlorium sulfate, barium carbonate, calcium carbonate, kaolin, silica, magnesium carbonate, alumina, and yellow lead, and phthalocyanine. Organic pigments or dyes such as azo-based pigments and azo-based pigments can be used.

Furthermore, dioctyl phthalate, diphenyl phthalate, tributyl phosphate, tricresyl phosphate, chlorinated paraffin sodium chloride (D-cho Vll agent may be used, and as paint additives, adhesives, dispersants, wetting agents, anti-sagging agents, etc.) It is also possible to use agents.

Hereinafter, the present invention will be explained in further detail with reference to Examples.

Table 3 shows the composition of the paint.

Among the paint compositions shown in Table 3, rosin (a) (resin (
C), inorganic antifouling agent (b), pigment, and additives are charged into an attritor and mixed, and a portion of the solvent is added to adjust the dispersion viscosity, and the particle size is adjusted while maintaining the dispersion temperature at 40 to 50'C. The mixture was dispersed for about 1 hour until the particle size was 3 μm or less, the remaining solvent was added, and the mixture was filtered to obtain antifouling coating compositions of Examples 1 to 16, Comparative Examples 1 to 3, and a base material of Comparative Example 4. In Comparative Example 4, a curing agent was further added at a ratio of 10 parts to 100 parts of the base resin to obtain an antifouling coating composition.

Note *1 Epoxy tree strength Dainippon Ink & Chemicals Co., Ltd. 12 Hydrocarbon resin (petroleum resin) Mitsui Petrochemical Co., Ltd.
Manufactured by 13 Chlorinated paraffin resin Manufactured by Toyo Soda Kogyo ■14
Kumaron resin manufactured by Nippon Steel Chemical Co., Ltd. 15 Urethane resin manufactured by Ap-Kagaku @ I6 Ethylene vinyl acetate copolymer manufactured by Showa Kobunshi Ω 17 Styrene butadiene 4-charcoal structure Go
od Yearsha Summer 19 Made by Dainippon Ink Chemical ■ #10 Phenol resin Made by Showa Union Synthetic ■ 111
Algite resin Manufactured by Mitsui Toatsu Chemical ■12 □ Kusumoto Kasei ■#13 Melamine resin Manufactured by Dainippon Ink & Chemicals ■11
4 Chlorinated rubber manufactured by Asahi Denka Kogyo ■115 Chloride/vinyl acetate copolymer manufactured by Tsukimizu Kagaku Kogyo ■16
Styrene resin Showa Kobunshi ■117 Urea resin Dainippon Ink & Chemicals ■118 Polyester resin Hitachi Chemical ■150 Acrylic resin Hitachi Chemical ■
Made #20 urethane resin Tokushima essential oil (KK) ff121
Polyamide Performance test made by Asahi Denka Kogyo @ ■ Rotary test A sandblasted 10 x 10 x 0.8 ■ steel plate was coated with etching primer once to a coating thickness of 5P, and then coated with m film of tarvinyl ship bottom anti-corrosion paint. Thickness 70μ
After coating once, the antifouling paint compositions of Examples 1 to 16 and Comparative Examples 1 to 4 were applied twice at a film thickness of 60%, and each of the test plates obtained was suspended below the sea surface. Mounted on the outside of a rotating drum, the drum tube was rotated so that the speed of seawater was 16 knots relative to the test plate, a rotary test was conducted for 3 months, and the difference between the initial film thickness and the film thickness after changes over time was measured. Part 3
The self-polishing property was evaluated by calculating the average value for 3 months.

The test results are shown in Table 4.

As is clear from Table 4, in Examples 1 to 16, the coating film was consumed at a rate of 2μ to 16μ per month and exhibited self-polishing properties, whereas Comparative Examples 1-4 showed self-polishing properties.
The coating film was not worn away at all, and there was no self-polishing property.

■ 29-, /3y test A coat of cool epoxy paint with a thickness of 125μ as an undercoat anti-corrosion paint was applied to a sandblasted 10X10XImA steel plate.
After coating twice, and further applying tar vinyl intermediate paint once to a coating thickness of 70μ, Examples 1 to 16 and Comparative Examples 1 to
The antifouling paint composition of No. 4 was applied twice to a film thickness of 60 μm, and each of the test plates obtained was subjected to the above-mentioned rotary test for one month, and then immersed in the sea at 1.5 fn for one month. A sea & ration test was conducted to simulate the operation of a ship, and the antifouling property for each cycle was expressed as the area occupied by the attached organisms on the test coating.

The test results are shown in Table 5.

As is clear from Table 5, there is no abnormality in Examples 1 to 16, except that Example 14 becomes soiled in the L55th year, and Examples 4.5 become soiled in the second year, respectively. On the other hand, in Comparative Examples 1 to 4, 5 to 10 units were soiled in 6 months, 25 to 80% in 1.5 years, and 50 to 90 units in 2 years.

As described above, it is clear that the present invention has self-polishing properties while being non-degradable, and as a result, excellent antifouling properties can be obtained, and is industrially useful.

Patent applicant: NOF Corporation

Claims (1)

[Scope of Claims] (e) A composition containing resin gold as a main component that is compatible with rosin, comprising: 1) a volume ratio of the sum of rosin (a) and inorganic antifouling agent (b) to resin (c); is 98:2 to 60:40,
and 11) the volume ratio of rosin (a) and resin (c) is 95
: Non-hydrolyzable self-polishing antifouling paint composition (2) characterized by a ratio of rosin (a) and resin (c') to an inorganic antifouling agent (b). The non-hydrolyzable self-polishing antifouling paint composition (3) according to claim 1, wherein the volume ratio is 95:5 to 40:60, the solubility parameter Sp value of the resin (e) is 7. ．．
Non-hydrolyzable self-polishing type antifouling paint composition according to Claims No. 0 to 120 Non-hydrolyzable self-polishing type antifouling paint composition Hydrolyzable self-polishing Type antifouling paint composition (6) The resin (c) is a radical polymerized resin, and when the distribution coefficient ψ of the resin for water and Octatool is P, its tog P is 1.4 or more. Non-hydrolyzable self-polishing antifouling paint composition (7) according to Claims 1, 2, 1, 3, 15, wherein the rosin (a) has an acid value of 120 or more, Melting point 40'0
The non-hydrolyzable self-polishing antifouling paint composition (8) inorganic antifouling agent, etc., as set forth in Claims No. 1-2, which has the above characteristics, has a solubility in seawater of o,
Non-hydrolyzable self-polishing type antifouling paint composition according to Claim No. 2, comprising IPPM to 10% (9) The inorganic antifouling agent (b) is cuprous oxide or copper thiocyanate. , zinc chromate, strontium chromate, and zinc oxide.