JPS58174452A - Antifouling paint composition having high storage stability - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent antifouling property, and high storage stability, free from the lowering of the dischargeability from the paint can for compounding and the deviation of the coating film thickness from the designed thickness caused by the thickening of the paint, and suitable for the antifouling coating of a ship's bottom, etc., by adding an ester compound having a specific functional group to a triorganotin-containing polymer and copper, etc. CONSTITUTION:The objective composition is prepared e.g. by adding (A) a compound of formula (R<1> and R<2> are H or 1-5C alkyl; R<3> is hydroxyl or acetyl; R<4> is 1-5C alkyl) (e.g. methyl acetoacetate) to (B) a triorganotin-containing polymer or copolymer obtained by the copolymerization of (i) a polymerizable unsaturated monobasic acid (e.g. acrylic acid) with (ii) a polymerizable unsaturated monomer (e.g. methyl methacrylate) and (B) copper or a copper compound (e.g. cuprous oxide). The amount of the triorganotin- containing polymer, etc. is 5-50wt% based on the solid component of the whole paint composition, and that of the component (A) is 0.1-100pts.wt. per 100pts.wt. of the solid component of the component (B). EFFECT:There is no deterioration of the coating properties such as ununiformity of film thickness, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a storage-stable antifouling coating composition.

In recent years, high-molecular organotin compounds containing organotin groups in their molecules have been used as excellent antifouling agents to prevent marine organisms from adhering to fishing nets and ship bottoms. In addition, by using a copper compound (e.g., cuprous oxide, copper rhodan) in combination with this polymeric organotin compound,
Furthermore, it is also known that a ship bottom paint has a high degree of antifouling performance.

However, antifouling paints made by mixing copper or copper compounds with high-molecular organotin compounds gradually increase in viscosity during storage, and in severe cases gel, resulting in stringiness, deviations in the designed film thickness, and film thickness defects. It causes uniformity and uncoating, which reduces the value of the product. Furthermore, paints that have thickened or gelled in this manner often show a decrease in antifouling performance.

As a result of intensive research, the present inventor has found that if an ester compound having a functional group is added during the production of a tri-organotin-containing polymer or copolymer or during the formulation of a paint.

The present invention was completed based on the discovery that excellent storage stability can be obtained even in the presence of copper or a copper compound.

That is, 9 the present invention provides (a) at least one (
7) An antifouling paint containing a triorganotin-containing polymer or copolymer having M -COO8nR, (in the formula represents an alkyl group, a cycloalkyl group, or a phenyl group) and Φ) copper or a copper compound as a main component. (C) general formula % formula % [wherein R1 and R2 may be the same or different, hydrogen atom or alkyl group having 1 to 5 carbon atoms + RF is hydroxyl group or acetyl group] base, W is 1
- an alkyl group having 5 carbon atoms] is added to the triorganotin-containing polymer or copolymer or at the time of formulating the antifouling paint. An antifouling paint composition having the following properties.

Examples of the ester compound having a functional group added in the antifouling paint composition of the present invention include 9.

Methyl acetoacetate/L/, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, amyl acetoacetate, methyl lactate, ethyl lactate, propyl lactate, butylacetate/L/,
Amyl lactate, α-hydroxybutyrate methi/L/, α-human. ethyl loquinbutyrate, methyl α-hydroxyisobutyrate,
Ethyl α-hydroxyisobutyrate.

Examples include α-hydroxymethyl acetate and α-hydroxyethyl acetate. One or more types of ester compounds having these functional groups can be added.

In the present invention, the triorganotin-containing polymer or copolymer contains at least one group -C0 (J8nR3
(Rid alkyl, cycloalkyl, or phenyl group) polymer or copolymer 1 For example,
A triorganotin-containing copolymer and an unsaturated acid obtained by copolymerizing a triorganotin salt of a dipolymerizable unsaturated basic acid or a polybasic acid with a polymerizable unsaturated monomer described in the publication No. A homopolymer of triorganotin salts.

■British Patent No. 1408327 and Japanese Unexamined Patent Publication No. 55-696
9, which is obtained by reacting a triorganotin compound with a high acid value vinyl resin obtained by copolymerizing a polymerizable unsaturated basic acid or a polybasic acid and a polymerizable unsaturated monomer, as described in Publication No. 62. tri-organotin-containing copolymer.

Examples include.

Here, the triorganotin group in the triorganotin-containing polymer or copolymer of the present invention includes cases where the organic group is an alkyl group, a cycloalkyl group, or a phenyl group having 1 to 8 prime numbers; Examples thereof include an alkyltin group, a tricyclo°.alkyltin group, and a triphenyltin group. Also above ■
Examples of the polymerizable unsaturated basic acids used in the method of ~■ include acrylic acid, methacrylic acid, and vinylbenzoic acid; examples of the 9-polymerizable unsaturated polybasic acids include maleic acid, itaconic acid, and their acid anhydrides; However, the polymerizable unsaturated supermers used in the copolymerization include, for example, methyl methacrylate, butyl methacrylate, chlorohexyl methacrylate, phenyl methacrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, and cyclohexyl acrylate. , phenyl acrylate, hydroxyethyl reacrylate, acrylic/L/based compounds, vinyl chloride, vinylidene chloride.

Acrylonitrile, methacrylonitrile, #vinyl acid,
Examples include vinyl lv compounds having functional groups such as vinyl butyrate, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, and lauryl vinyl ether, and vinyl hydrocarbons such as ethylene, butadiene, and styrene.

One type or two or more types of polymerizable unsaturated monomers may be used.

Other copper or copper compounds constituting the antifouling paint of the present invention include metallic copper, copper alloys, and cuprous oxide.

Examples include copper rhodan, copper phosphide, copper rosinate, copper naphthenate, copper hydroxide, and especially cuprous oxide.

Rodan steel is preferred.

The content of each component of the antifouling paint of the present invention is such that the tri-organotin-containing polymer or copolymer has a content of 5 to 5 to 50% of the total solid content of the paint.
50% by weight of copper or copper compounds.

It can be 10 to 70% by weight.

It is added to the antifouling paint of the present invention. The amount of the ester compound having a functional group added is 0.1 to 100 parts by weight per 100 parts by weight of the triorganotin-containing polymer or copolymer (as solid content).
Parts by weight, preferably 1 to 20 parts by weight. The ester compound having a functional group may be added in advance during the production of the triorganotin-containing polymer or copolymer, or may be added immediately after production, or may be added at the stage of forming a coating.

The antifouling coating composition of the present invention thus obtained can maintain long-term storage stability. As a result, disadvantages due to thickening 9, such as poor pouring when blending paint,
Problems such as deviations in the designed film thickness after blending the paint, deterioration of paintability such as non-uniformity of the film thickness, etc. can be completely eliminated, and the product value can be maintained. It is also possible to always exhibit excellent antifouling performance.

The antifouling paint composition of the present invention thus obtained is ready to use!
Dissolved in organic solvent, or pigment, carrier.

Plasticizers, paint conditioners, other resins (e.g. methyl methacrylate/butyl methacrylate/butyl acrylate polymers) and poorly soluble substances (e.g. low molecular weight bolybdenum, chlorinated paraffins) toxic elution regulators (retardants or accelerators) ), and other antifouling agents as necessary (for example, triorganotin compounds such as tributyltin fluoride, tributyltin oxide, triphenyltin fluoride, and organic compounds such as thiuram disulfide dimethyl dithiocarbamate).

Used together with a diluent in antifouling paints for ship bottoms.

The present invention will be explained below with reference to Production Examples, Examples, and Test Examples. In each example, the middle part indicates parts by weight, and 6% indicates weight %.

Production example of tri-organotin-containing copolymer Production example A ・In a 1T flask equipped with a thermometer and stirring 1,
'f/Vtin, Gakjl V-) 13(1,)ft
v) P') Lylate 70F, benzoyl peroxide 1.52 and xylene 200F were polymerized at 85 to 90°C for 8 hours. The obtained tributyltin-containing copolymer solution had a viscosity (25° C.) of 820 cps, and its heating residue was 49.8%.

Production Example B Tributyltin methacrylate 1 was prepared using the same equipment as Production Example A.
20 F, methyl methacrylate 60 F, 2
-ethylhexyl methacrylate)209. Azobisisobutyronitrile 1.52 and xylene 2002 from 75 to
Polymerization was carried out at 80°C for 8 hours. The obtained tributyltin-containing copolymer solution had a viscosity (25° C.) of 78° cps, and its heating residue was 49.9%.

Production Example C Tributyltin methacrylate 1 was prepared using the same equipment as Production Example A.
30 F, methyl methacrylate V-)? Of', methyl lactate 209 was added to 1.5f of benzoyl peroxide and 187f of xylene, and polymerization was carried out at 85 to 90°C for 8 hours.The obtained tributyltin-containing copolymer solution had a viscosity (at 25°C). 8-50 cps, and its heating residue was 49.6%.

Production example fc1 equipped with a thermometer, a stirrer, a dropping funnel and a reflux dehydrator.
In a T flask, 27.5 tons of methacrylic acid, 60F of methyl methacrylate, and 2Of of 2-ethylhexyl acrylate.
, Add 1.5f of benzoyl peroxide, ethyl lactic acid/L/40F and 160t of xylene and heat to 85-90°C.
Polymerization was carried out for 8 hours. Next, bis(tributyltin)
Oxide was added dropwise at 85 to 90°C over 1 hour, and after stirring for 2 hours, reflux dehydration was performed at 100 to 110°C under reduced pressure for 1 hour. The tributyltin copolymer solution obtained had a viscosity (25°C) of 730 cps.

The heating residue was 49.9%.

Examples 1 to 8 - To the thin liquid of the triorganotin-containing copolymer obtained in Production Examples A to D,
A copper compound, an ester compound having a functional group (already contained in the copolymers obtained in Production Examples C and D), a pigment 9 dispersant (hydrogenated castor oil-amite type), and a solvent were added. A ship bottom antifouling paint was manufactured by blending the ingredients in the proportions shown in Table 1.

Comparative Examples 1-2 Tori containing no Nether compound having a functional group Storage stability test Each of the antifouling paints obtained in Examples 1-8 and Comparative Examples 1-2 was poured into two 200-capacity round metal cans. put in.

One of them was stored in an air oven at 50°C for two weeks, and the other one was left at room temperature for six months.

The viscosity changes of each were investigated. The viscosity was measured in a constant temperature bath at 25°C. The results are shown in Table 2.

B Antifouling test Sand gel blasted mild steel plate (300X 100X 2
(m) was coated with commercially available ship bottom paint No. 1 twice to give a total dry film thickness of 100p. This was coated with Examples 1 to 8 and Comparative Examples 1 to 2, and after being left at 50° C. for 2 weeks, each coating was applied to a dry film thickness of 100 μm. After drying each coated plate at room temperature for one week, a dipping test was conducted in Owase Bay, Mie Prefecture, and observations were made periodically.

The results are shown in Table 3.

Table 2 Table 3 (Note) The symbols in the table indicate the following.

○ mark: No marine animals and plants attached △ mark: // Adhesive reeds, 20% or less × mark:
〃 Adhesive, 205 or more patent applicant Nichizuka Kasei Co., Ltd. Representative Patent attorney Tetsuya Matsunaga □ 11

Claims (1)

[Claims] 1. (a) At least one group -COO8n in the molecule
R3 (in the formula, R is a←kyl group, cycloalkyl M or /li
In an antifouling paint containing a triorganotin-containing polymer or copolymer having 7 enyl group) and Φ) copper or a copper compound as a main component, (C) the general formula % formula % [in the formula R1 and R2 may be the same or different, and R2 is a hydrogen atom or a sulfalkyl group having 1 to 5 carbon atoms +) CI'' is a hydroxyl group or a 7-cetyl group,
R4 represents an alkyl group having 1 to 5 carbon atoms] is added to the triorganotin-containing polymer or copolymer or when formulating the antifouling paint. An antifouling paint composition with storage stability.