Coated bis (2-pyridinethiol-1-oxide) copper salt

Compositions – Preservative agents – Anti-corrosion

Reexamination Certificate

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Details

C252S400530, C252S088100, C252S182330, C106S016000, C106S017000, C106S018330

Reexamination Certificate

active

06630079

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a composition containing an antifouling active ingredient for a coating for the bottom of a ship, which is safe during handling (e.g., transport) and coating operation and which is superior in an antifouling effect.
BACKGROUND ART
A bis(2-pyridinethiol-1-oxide) copper salt is effective as an industrial biocide and has been drawing much attention in recent years as a substitute antifouling active ingredient for organic tin.
The salt is in the form of fine and stiff needle-like crystals and tends to scatter as powder dust. This compound does not cause much irritation to a worker's fingers or hands upon contact, but when it comes into contact with the mucous membrane of nose, eye, trachea, lung and the like, it causes strong irritation. Particularly, when it is inhaled into the lung in a large amount, more serious disorders may be caused by the stiff needle crystals. To prevent this, workers should be extremely cautious not to inhale the compound or to allow adhesion thereof to the eye, skin, or clothes. For this end, workers put on suitable protective equipments, such as a dust preventive mask, protective glasses, protective gloves, protective clothes and the like, during handling of this compound. In addition, a local exhaust system is installed so as not to contaminate the work environment with the powder dust. However, the above-mentioned countermeasures are not sufficient to completely prevent workers from being exposed to the scattered powder dust. What is worse, these countermeasures strikingly lower the work efficiency.
DISCLOSURE OF THE INVENTION
The present invention aims at solving these problems and provides a composition containing a bis(2-pyridinethiol-1-oxide) copper salt, which is an antifouling component of a coating for the bottom of a ship and which is free from an adverse influence on the effectiveness of the compound.
The present inventors have conducted intensive studies in an attempt to solve the above-mentioned problems of the conventional bis(2-pyridinethiol-1-oxide) copper salt, and arrived at the coated bis(2-pyridinethiol-1-oxide) copper salt of the present invention. That is, they have found that coating of the bis(2-pyridinethiol-1-oxide) copper salt with a specific coating agent suppresses scattering of the powder dust, which in turn improves safety of the worker and work performance, and that a coating for the bottom of a ship, which contains this coated bis(2-pyridinethiol-1-oxide) copper salt, shows a stable effect for a long time without an adverse influence on the antifouling effect and shows the same stability during a long-term storage, which resulted in the completion of the present invention.
Accordingly, the present invention provides the following.
[1]: A bis(2-pyridinethiol-1-oxide) copper salt coated with a coating agent containing one or more kinds of compounds selected from the group consisting of glycerin, dialkyl phthalate, lubricating oil, acrylic resin, rosin, fatty acid amide, dialkyl polysulfide, polybutene, paraffin and petrolatum.
[2]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the glycerin, dialkyl phthalate, lubricating oil, acrylic resin, rosin, fatty acid amide, dialkyl polysulfide, polybutene, paraffin or petrolatum is contained in an amount of 1-40 parts by weight per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[3]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [2], wherein the amount of the one or more kinds of compounds selected from the group consisting of glycerin, dialkyl phthalate, lubricating oil, acrylic resin, rosin, fatty acid amide, dialkyl polysulfide, polybutene, paraffin and petrolatum is 1-40 parts by weight in total per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[4]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of glycerin per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[5]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of dialkyl phthalate per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[6]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of a lubricating oil per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[7]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of an acrylic resin per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[8]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of rosin per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[9]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of fatty acid amide per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[10]: A composition containing the coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of dialkyl polysulfide per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[11]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of polybutene per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[12]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of paraffin per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
[13]: The coated bis(2-pyridinethiol-1-oxide) copper salt of [1], wherein the bis(2-pyridinethiol-1-oxide) copper salt is coated with 1-40 parts by weight of petrolatum per 100 parts by weight of the bis(2-pyridinethiol-1-oxide) copper salt.
The bis(2-pyridinethiol-1-oxide) copper salt is known as a compound superior in antifouling property due to its biocidal effect and is used as an antifouling component of a coating for marine craft and the like, such as a coating for the bottom of a ship and the like. This copper salt is commercially available and can be produced by the method disclosedin, for example, U.S. Pat. No. 2,809,971.
The bis(2-pyridinethiol-1-oxide) copper salt is coated with a coating agent containing one or more kinds of the compounds selected from the group consisting of glycerin, dialkyl phthalate, lubricating oil, acrylic resin, rosin, fatty acid amide, dialkyl polysulfide, polybutene, paraffin and petrolatum.
Examples of glycerin include diglycerin, polyglycerin and the like, besides typically used glycerin. These may be used in admixture.
The alkyl moiety of dialkyl phthalate preferably has 1 to 18 carbon atoms. Examples thereof include diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and the like. These may be used in admixture.
Examples of lubricating oil include spindle oil, dynamo oil machine oil, engine oil, turbine oil, silicon oil and the like. These may be used in admixture. Other hardly volatile substances, such as higher alcohols (e.g., polyethylene glycol, stearyl alcohol and the like) and the likemay be used concurrently.
Examples of acrylic resin include homopolymers and copolymers of acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acryl

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