JP4037772B2 - (4-Isopropylpyridinio) methyldiphenylboron-containing composition with improved stability - Google Patents

Description

ＯＡＭ：ｎ−オクチルアミン、ＥＨＡＭ：２−エチルヘキシルアミン、ＤＤＡＭ：ｎ−ドデシルアミン、ＯＤＡＭ：ｎ−オクタデシルアミン、ＨＡＭ：ｎ−ヘキシルアミン、ＴＣＰ：トリクレジルホスフェート、ＩＰＡ：イソプロピルアルコール
※比較例３は、アミン臭が強く塗布作業が困難であった。
【００２０】
実施例７ 漁網防汚塗料
ＩＰＭＢ４質量部（以下同じ）、ｎ−オクタデシルアミン３．５部、アクリル樹脂ワニス５部、ポリブテン５部、ポリオキシエチレン変性シリコーン２部及びキシレン６０．５部をボールミルによって分散処理して漁網防汚塗料を得た。
【００２１】
次に、試験例を挙げて、本発明の効果を説明する。
試験例１
サンドブラスト処理鋼板に予め通常の防錆塗料を塗布した後、その乾燥塗膜上に、３０℃で３０日間保存した実施例１〜６及び比較例１〜４の塗料を、１５０ｇ／ｍ²／回の塗装量で２回刷毛塗りして試験板（１００ｍｍ×３００ｍｍ）を作った。この試験板を、三重県尾鷲市尾鷲湾内において、深度１．５ｍの海中に１８ヶ月間浸漬し、表２に示した期間ごとに水棲生物の付着面積及び付着生物を観察した。その結果を表２に示す。表２には、塗膜中の活性成分の含有理論量をｇ／ｍ²でそれぞれ示した。
【００２２】
また、付着面積の判定基準は、次によった。
５：付着なし
４：付着生物５％未満の付着
３：付着生物５〜２０％未満の付着
２：付着生物２０〜５０％未満の付着
１：付着生物５０％以上の付着
【００２３】
表２中の生物の付着状況は、次を意味する。
−：付着なし
ａ：フジツボが付着
ｂ：フジツボ、セルプラが主に付着
ｃ：フジツボ、セルプラ、ムラサキイガイ等の貝類に、アオサ、アオノリ等の藻類が付着
【００２４】
【表２】

表２から明らかなように本発明の組成物は、長期に亘り生物の付着を防止することが判る。
【００２５】
【発明の効果】
本発明の組成物は、有効成分であるＩＰＭＢの安定性に優れ、長期に亘ってその効力が持続する。例えば、水中防汚塗料として使用した場合、水中構築物、船舶等に塗布することにより、水棲生物であるフジツボ、ホヤ、セルプラ、ムラサキイガイ、アオサ、アオノリ等の付着を長期間に亘って防止でき、優れた防汚効果を発揮する。そして、本発明の防汚塗料の防汚効果は、従来多用される防汚性有効成分化合物に比べ、遙かに上回るものである。また、本発明の防汚塗料に配合される特定の第一級アルキルアミンは、人畜、魚介類に低毒性であり、安全に使用できる。また、この塗料は、長期間貯蔵しても効果を失うことなく使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to (4-isopropylpyridinio) methyldiphenylboron-containing compositions with improved stability.
[0002]
[Prior art]
(4-Isopropylpyridinio) methyldiphenylboron is used as an active ingredient in compositions such as underwater antifouling agents, bactericides / fungicides, insecticides, acaricides (for example, Patent Document 1 and Patents) Reference 2).
[0003]
However, (4-isopropylpyridinio) methyldiphenylboron has a problem of low stability when dissolved in a solvent and in a mixed system such as a paint. In addition, it is not economical to use at a high dose, and there is a problem in terms of environmental protection.
[0004]
[Patent Document 1]
Japanese National Patent Publication No. 11-500747 [Patent Document 2]
Japanese Patent Laid-Open No. 7-138265
[Problems to be solved by the invention]
An object of the present invention is to improve the stability of a composition such as an underwater antifouling agent, a bactericidal / fungicidal agent, an insecticidal agent or an acaricide containing (4-isopropylpyridinio) methyldiphenylboron. .
[0006]
[Means for Solving the Problems]
The present invention includes the following inventions.
(1) A composition comprising (4-isopropylpyridinio) methyldiphenylboron and a primary alkylamine having 8 to 18 carbon atoms.
(2) The composition according to (1) above, which is an underwater antifouling coating composition.
(3) The composition according to (2) above, which is a fishing net paint.
(4) The composition according to any one of (1) to (3), wherein the primary alkylamine is octadecylamine or dodecylamine.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
(4-Isopropylpyridinio) methyldiphenylboron (hereinafter referred to as “IPMB”) used in the present invention is obtained by known methods such as ethanolamine diphenylborate according to the method described in JP-A-7-138265. It can be prepared by reacting an ester with methylmagnesium halide and then with 4-isopropylpyridine.
[0008]
Examples of the primary alkylamine having 8 to 18 carbon atoms used in the present invention include a linear or branched primary alkylamine having an alkyl group having 8 to 18 carbon atoms, such as n-octylamine, 2 -Ethylhexylamine, 3-ethylhexylamine, 2,2-dimethylhexylamine, 2,3-dimethylhexylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine is mentioned. When the carbon number of the primary alkylamine is 7 or less, for example, n-hexylamine and n-heptylamine have a strong odor and are difficult to work on, for example, with amines having 19 or more carbon atoms, It is not preferable from the viewpoint of paint properties, particularly coating film properties.
[0009]
IPMB is usually blended in a composition such as a liquid composition or a paint at 1 to 30% by weight, preferably 3 to 10% by weight. The primary alkylamine is added in a molar ratio with respect to IPMB and usually 0.5 to 2, preferably 0.8 to 1.5 with respect to 1 of IPMB. If the addition ratio of the primary alkylamine is less than 0.5, the effect of IPMB after long-term storage, for example, the antifouling effect decreases, while if it exceeds 2, the stability and antifouling properties are further exceeded. I cannot expect improvement.
[0010]
The composition of the present invention improves the stability of IPMB in a conventional IPMB-containing composition having a problem in stability, and the use thereof is particularly limited as long as it is a composition containing IPMB as an active ingredient. The form includes, for example, a liquid composition (for example, a solution or a suspension) that does not contain a paint and a film-forming resin.
[0011]
The composition of the present invention can be produced in the same manner as an ordinary IPMB-containing composition except that the primary alkylamine is blended.
For example, the paint of the present invention (for example, an antifouling paint) can be produced according to a usual paint production method, and IPMB and the primary alkylamine are blended, and this is combined with a paint resin, a solvent, and necessary. Thus, a coloring pigment, an extender pigment, various paint additives, etc. are appropriately blended, and after being roughly dispersed and dissolved with a dissolver or the like, it can be obtained by uniformly dispersing with a disperser such as a dyno mill, a sand mill or a ball mill if necessary. it can.
[0012]
The paint resin that can be used in the paint of the present invention is a film-forming resin for forming a paint film on the surface of the substrate, and the same resins as those of conventional paints can be used. For example, the resin includes vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl isobutyl ether copolymer resin, styrene-butadiene copolymer resin, chlorinated rubber resin, chlorinated polypropylene resin, petroleum resin. Alkyd resins, acrylic resins, synthetic rubbers, epoxy resins, silicone rubbers, silicone resins, rosins, and mixtures thereof.
[0013]
Moreover, a solvent can be mix | blended in order to adjust the viscosity of a coating material. The kind of solvent to be used is not particularly limited as long as it can dissolve the resin for paint. Examples of the solvent include alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and ethylene glycol, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and cumene, ethers such as dioxane and tetrahydrofuran, and methyl ethyl ketone. , Ketones such as cyclohexanone and methyl isobutyl ketone, esters such as butyl acetate, ethylene glycol acetate and amyl acetate, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, aliphatic or alicyclic hydrocarbons Examples include cyclohexane and the like, as well as petroleum fractions such as solvent naphtha and kerosene.
[0014]
Examples of the color pigment include titanium white, red rose, carbon black, cyanine blue, and cyanine green. Examples of the extender pigment include talc, barita, and calcium carbonate. Furthermore, as additives for coatings, precipitation inhibitors such as polyamide, antifoaming agents such as silicone, chemical elution aids such as modified silicone and surfactant, and plasticizers such as tricresyl phosphate and chlorinated paraffin, etc. Can be mentioned.
[0015]
Furthermore, the paint of the present invention may be used in combination with an active ingredient other than IPMB, for example, in the case of an antifouling paint, in combination with other known antifouling agents, for example, tetramethylthiuram. Disulfide, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 3-iodo-2-propynylbutylcarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino- s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, N- (fluorodichloromethyl) Thio) phthalimide, N, N-dimethyl-N ′-(fluorodichloromethylthio) -N′-phenylsulfamide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, 2 , 3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, diiodoparatolylsulfone and the like may be blended in an arbitrary ratio and used in a normal coating production method. it can.
[0016]
The paint of the present invention prepared in this manner is used as it is or after adjusting the viscosity with a solvent, and usually by airless spray coating, sometimes by roller coating, brush coating, etc. And used for marine structures with a dry film thickness of about 30-300 μm. Further, as a fishing net antifouling agent, it is preferable to use it as a clear antifouling paint without blending a pigment or the like.
[0017]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited by these. The numbers in Table 1 are parts by mass.
[0018]
Examples 1 to 6 and Comparative Examples 1 to 4
Each component shown in Table 1 was dispersed by a ball mill to obtain a uniform coating composition (Example). Similarly, a comparative paint (comparative example) was also obtained. In Examples and Comparative Examples, varnish 1 represents a 50% xylene solution of acrylic resin varnish, and varnish 2 represents a 60% xylene solution of rosin varnish. As the suspending agent, Disparon 6900-20X (manufactured by Hashimoto Kasei Co., Ltd.) was used.
[0019]
[Table 1]

OAM: n-octylamine, EHAM: 2-ethylhexylamine, DDAM: n-dodecylamine, ODAM: n-octadecylamine, HAM: n-hexylamine, TCP: tricresyl phosphate, IPA: isopropyl alcohol * Comparative Example 3 Had a strong amine odor and was difficult to apply.
[0020]
Example 7 Fishing net antifouling paint IPMB 4 parts by mass (hereinafter the same), n-octadecylamine 3.5 parts, acrylic resin varnish 5 parts, polybutene 5 parts, polyoxyethylene-modified silicone 2 parts and xylene 60.5 parts by a ball mill Dispersion treatment was performed to obtain a fishing net antifouling paint.
[0021]
Next, a test example is given and the effect of this invention is demonstrated.
Test example 1
After pre-coated with normal anticorrosive paint sandblasted steel sheet, its on dried coating, the Examples 1-6 and Comparative Examples 1-4 paint was stored for 30 days at 30 ℃, 150g / m ² / dose A test plate (100 mm × 300 mm) was made by brushing twice with the coating amount of This test plate was immersed in the sea of 1.5m depth in Owase Bay, Owase City, Mie Prefecture for 18 months, and the attached area and attached organisms of aquatic organisms were observed every period shown in Table 2. The results are shown in Table 2. Table 2 shows the theoretical content of the active ingredient in the coating film in g / m ² .
[0022]
Moreover, the criteria for determining the adhesion area were as follows.
5: No adhesion 4: Adhesion organism less than 5% adhesion 3: Adhesion organism less than 5-20% adhesion 2: Adhesion organism less than 20-50% adhesion 1: Adhesion organism more than 50% adhesion [0023]
The status of organism attachment in Table 2 means the following.
-: No adhesion a: Barnacles adhere b: Barnacles, cell plastics mainly adhere c: Algae such as Aosa, Aonori adhere to shellfish such as barnacles, cell plastics, mussels
[Table 2]

As is apparent from Table 2, it can be seen that the composition of the present invention prevents the attachment of organisms over a long period of time.
[0025]
【The invention's effect】
The composition of the present invention is excellent in the stability of IPMB, which is an active ingredient, and maintains its efficacy over a long period of time. For example, when used as an underwater antifouling paint, by applying it to underwater structures, ships, etc., it is possible to prevent adhesion of aquatic organisms such as barnacles, squirts, cell plastics, mussel, Aosa, Aonori, etc. over a long period of time. Demonstrates antifouling effect. The antifouling effect of the antifouling paint of the present invention is far greater than the antifouling active ingredient compounds that are frequently used in the past. Moreover, the specific primary alkylamine blended in the antifouling paint of the present invention has low toxicity to human livestock and fishery products and can be used safely. In addition, the paint can be used without losing the effect even when stored for a long time.

Claims (4)

A composition containing (4-isopropylpyridinio) methyldiphenylboron and a primary alkylamine having 8 to 18 carbon atoms. The composition according to claim 1, which is an underwater antifouling paint composition. The composition according to claim 2, which is a fishing net paint. The composition according to any one of claims 1 to 3, wherein the primary alkylamine is octadecylamine or dodecylamine.