JPH07166106A - Polyester resin composition for antifouling coating - Google Patents

Abstract

PURPOSE:To obtain a polyester resin composition for antifouling coating excellent in hydrolysis rate, physical properties of coating film, solubility to solvents, etc., and excellent in alga-proof property and shellfish-preventing property. CONSTITUTION:This polyester composition for antifouling coating uses an aliphatic polyester obtained by copolymerizing at least one kind of compound selected from glycerin, ethylene glycol and 1,4-butanediol into a polyester consisting of succinic acid and 1,2-propylene glycol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for antifouling paint which is excellent in algae resistance and shell resistance. Seaweeds and shellfish adhere to materials used in the sea, such as the bottoms of vessels sailing in the ocean, fishing nets for aquaculture, and ropes and buoys that determine their position, increasing the navigation resistance of the vessel, This causes problems such as reduced efficiency, reduced strength of materials and damage.

Damage caused by the adhesion of these algae and shellfish is not limited to this, and seaweeds and shellfish are attached to pipes and intake / discharge facilities of various industrial plants such as the inner wall of the intake pipe for cooling water of the nuclear power plant. It also causes problems such as waves, loss due to increase in tidal current resistance, damage, and deterioration of intake and drainage capacity. The polyester resin composition for antifouling paints of the present invention provides an antifouling paint applied to prevent the adhesion of seaweeds and shellfish as described above.

[0003]

2. Description of the Related Art Conventionally, in order to prevent the adhesion of seaweeds and shellfish of this kind as described above, antifouling agents such as organic tin and cuprous oxide have been compounded in hydrolyzable acrylic resins. I applied it.

In particular, a hydrolyzable acrylic resin of the type pendant with TBTO has been widely used because it has good long-term antifouling properties, but due to environmental problems in recent years, the legality has become stronger and the use of the TBTO pendant acrylic resin is difficult. Has become. For this reason, paint manufacturers and resin manufacturers are developing various types of hydrolyzable acrylic resins, and commercialization of silyl ester pendant acrylic resins is being promoted.

However, since the water-soluble acrylic resin is considered to have low biodegradability, marine pollution due to this acrylic resin is also considered, and it cannot be said to be an ideal resin. Therefore, when polyester is used, it is considered that the polyester changes into a monomer by hydrolysis and is easily incorporated into metabolic processes of microorganisms and the like as compared with an acrylic polymer.

As a hydrolyzable polyester for antifouling paints, a hydrolyzable resin in which a metal salt is introduced into the main chain of polyester (Japanese Patent Laid-Open No. 58-67722) has been studied, but the hydrolysis rate, coating film physical properties However, a resin satisfying all the requirements such as solubility in organic solvents has not been obtained.

[0007]

In view of the above circumstances, the present invention satisfies all performances such as hydrolysis rate, coating film physical properties and solvent solubility as a hydrolyzable polyester resin for antifouling paint. Provided is a polyester resin composition for antifouling paint.

[0008]

The present invention provides a polyester comprising succinic acid and 1,2-propylene glycol, and at least one selected from glycerin, ethylene glycol and 1,4-butanediol. The present invention relates to a polyester resin composition for antifouling paint, which comprises using an aliphatic polyester obtained by copolymerizing the above as a hydrolyzable resin.

The succinic acid and 1,2-propylene glycol used in the present invention are both food additives and safe substances for the environment, and polyesters composed of these are suitable for the hydrolysis rate and It has solubility in general-purpose solvents. For this reason, it is promising as a resin for antifouling paints, but on the other hand, since Tg is low, tack is likely to remain in the coating film, and it is not suitable as a resin for paints.

As a result of intensive studies to solve such a drawback, succinic acid and 1,2-propylene glycol-
There is no tack by moderately branching by copolymerizing a specific glycerin in a polyester made of polyester, or by imparting crystallinity by copolymerizing ethylene glycol, 1,4-butanediol, etc. The present invention has been completed by finding that a resin having a different hydrolysis rate can be obtained.

The molecular weight of the polyester resin for antifouling paints of the present invention must be 5,000 or more, preferably 10,000 or more, in consideration of the physical properties of the coating film. However, in consideration of coating suitability, it is necessary to be 100,000 or less, preferably 50,000 or less. The molecular weight in the present invention means a polystyrene-equivalent number average molecular weight measured by GPC.

The above polyester can be produced by a known method such as transesterification or dehydration polycondensation. Further, by mixing the polyester in the present invention with a polymer such as polyvinyl alcohol, polyoxyalkylene glycol, polydioxane, polyamino acid, or an inorganic substance such as talc, calcium carbonate, barium carbonate, various physical properties and decomposition characteristics of the film can be changed. It is possible.

When adjusting the resin of the present invention to an antifouling paint, if necessary, an antifouling agent such as cuprous oxide, zinc dimethyldithiocarbamate, tetramethylthiuram disulfide, a pigment, or a viscosity adjusting agent may be used. Blend. Hereinafter, details of the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0014]

【Example】

Example 1 Polymerization: PES-1 100 parts by weight of succinic anhydride (hereinafter abbreviated as “part”),
1,2-propylene glycol 84 parts, ethylene glycol 68 parts, glycerin 5 parts, esterification catalyst TBT
0.1 part of (tetra-n-butyl titanate) was charged into a four-necked flask, esterification was carried out at 180 ° C., and after confirming that 18 parts of water had been distilled off, polymerization was carried out at 240 ° C. and 1 mmHg. The polyester composition is shown in Table 1.

Preparation of paint: Paint (1) 100 parts of the above polyester (PES-1) was dissolved in 100 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) and 100 parts of toluene, and 100 parts of cuprous oxide was mixed to prepare a paint ( 1) was obtained.

Evaluation: Paint (1) The above paint (1) was coated on a 7 × 15 cm FRP plate with an airless spray to a wet thickness of 200 μm, and fixed on a metal frame made of stainless steel with a wire, and the surface of water in Yaizu Bay, Shizuoka Prefecture. It was immersed in a lower portion of 1.5 m to visually evaluate the amount of attached organisms, and the evaluation was performed in five levels. The results are shown in Table 2.

Example 2 Polymerization: PES-2 100 parts of succinic anhydride, 140 parts of 1,2-propylene glycol, 30 parts of 1,4-butanediol, 5 parts of glycerin, 0.1 part of TBT, 4 mouths Put in a flask, 180
After esterification at ℃ and confirming that 18 parts of water was distilled off, 24
Polymerization was performed at 0 ° C. and 1 mmHg. The polyester composition is shown in Table 1.

Preparation of paint: paint (2) 100 parts of the above polyester (PES-2) was added to MEK10.
It was dissolved in 0 parts and 100 parts of toluene, and 100 parts of cuprous oxide was blended to obtain a paint (2).

Evaluation: Paint (2) The same evaluation as in Example 1 was carried out. The results are shown in Table 2.

Comparative Example 1 Polymerization: PES-3 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 136 parts of ethylene glycol and 229 parts of neopentyl glycol were placed in a four-necked flask, T
0.1 part of BT was added and transesterified by stirring at 180 ° C. under normal pressure, 128 parts of methanol was distilled off, and then depressurized to polymerize at 1 mmHg and 240 ° C. to produce polyester (PES-3). ) Got. The polyester composition is shown in Table 1.

Preparation of paint: Paint (3) 100 parts of the above polyester (PES-3) was added to MEK10.
It was dissolved in 0 parts and 100 parts of toluene, and 100 parts of cuprous oxide was blended to obtain a paint (3).

Evaluation: Paint (3) The same evaluation as in Example 1 was carried out. The results are shown in Table 2.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

EFFECTS OF THE INVENTION As is clear from the results shown in Table 2, a polyester resin composition for antifouling paint having excellent anti-biofouling property was obtained by the present invention.

Claims (1)

[Claims] 1. Succinic acid and 1,2-propylene glycol
An aliphatic polyester obtained by copolymerizing at least one selected from glycerin, ethylene glycol and 1,4-butanediol in a polyester consisting of a polyester is used as a hydrolyzable resin. Polyester resin composition for dirty paint.