JPH03190975A - Antifouling coating composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject composition having long gel time and excellent coating ability to a substrate and effective in preventing the adhesion of shells and seaweeds in sea water by using an inorganic copper (compound), a specific resin, etc., in combination with a polymer containing acetoacetyl group. CONSTITUTION:The objective composition is produced by mixing (A) an inorganic copper compound and/or metallic copper with (B) a resin or a fatty acid having a molecular weight of <=3,000 and containing one carboxyl group in the molecule and adding (C) a polymer having acetoacetyl group to the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a so-called antifouling paint that prevents the adhesion of marine organisms such as shellfish and seaweed in the sea.

[Conventional technology and issues]

Preventing marine organisms from adhering to ship bottoms or underwater structures is extremely important for efficient operation and maintenance management. As a countermeasure against this problem, paints containing organic tin have been used as an effective solution. However, in recent years, the accumulation of organotin compounds mainly in fish has become a problem, and it has become difficult to use them as antifouling agents from the standpoint of public health. On the other hand, as an alternative to these organic tin-based paints, the use of inorganic copper compounds, mainly cuprous oxide, which does not accumulate in fish and has been used for a long time, is attracting attention again.

However, as is well known in the past, polymers such as 1-phenyltin methacrylate (1) have a function similar to that of ``eel paints'' in which they flow out from the surface in very small amounts in water, for example. It is said that it is difficult to obtain a patent that features cuprous oxide, which is an inorganic copper compound.

Paints that use copper monoarsenite as an antifouling agent and rosin as a vehicle are subject to severe wear and tear in seawater, and do not have long-term antifouling effects; It is said that the antifouling effect of the dirty paint disappears if cuprous oxide is distributed on the surface and the cuprous oxide is eluted.

8-1 In order for a coating film containing cuprous oxide to exhibit antifouling effect,
]μ9/can2/It is said that there should be no elution of zinc f arsenic, and it is necessary to maintain this value at a constant value over a long period of time, which is essential for an antifouling paint that works stably. Become something.

Numerous studies have been carried out in order to obtain vehicles for paints in which cuprous oxide is required, and the surface coating is continually renewed in such a way that it can supply a sufficient amount of cuprous oxide. .

Among them are monomers that form water-soluble polymers,
For example, there are examples in which hinylvirolitone is used as one component of the copolymer, or examples in which a monomer having a tertiary amino group is used.

However, existing antifouling paints that use these polymers as vehicles do not exhibit any change in physical properties depending on the environment in which they are used.
In other words, there is no oral change in the solubility of the polymer.

A desirable trend is to update the previously mentioned trend of paints so that the surface polymer, which does not contain cuprous oxide, always supplies a constant amount of cuprous oxide.

The present inventors have studied a vehicle that uses an inorganic copper compound such as cuprous oxide as an antifouling agent and releases a sufficient amount of copper ions to exhibit antifouling effects over a long period of time. It has been found that the object can be achieved by using a polymer having ace1 to acedel groups as at least one component.

In particular, it has been found that when a polymer having an ace-1-acetyl group is blended with a resin or fatty acid having one carboxyl group in the molecule, such as rosin, there is a long-term antifouling effect7. 'S.

However, when an antifouling paint using a polymer having acetylacetyl groups as a vehicle is used in combination with or mixed with an inorganic copper compound such as cuprous oxide, it remains paintable for a period of time, but eventually it becomes like a kelp. It may happen. In particular, multi-component copolymers that share carboxyl groups and/or hydroxyl groups (including acetoacetyl groups, hereinafter referred to as reactive functional groups) with acetoacetyl groups can, in extreme cases, turn into a keloid within a few minutes. It was also found that Therefore, in order to improve the workability of these antifouling paints, it is desirable to extend their pot life as much as possible.

The present inventors have conducted extensive studies to find a state in which these multi-component polymers having reactive functional groups and cuprates represented by cuprous oxide can be mixed together over a sufficient period of use. Surprisingly, if a compound having one carboxyl group in the molecule, such as 17-gin, and cuprous oxide are sufficiently kneaded in advance, this kneaded product can be added to a polymer having a reactive functional group. It was discovered that the gel state did not occur immediately even if
Another object of the invention has been achieved.

[Failure to solve the problem]

That is, in one aspect of the present invention, (a) nothing (
(b) A resin or fatty acid having a molecular weight of 3 ooo or more and having one carphokidyl group in the molecule, and (c) a polymer having an acetyl group. The present invention provides an antifouling paint silk paste.

Yet another aspect of the invention provides that (a) an inorganic copperide and/or copper; and (b)) a molecule i 3000
An antifouling paint composition characterized in that: (1) a resin or a fatty acid having one carboxyl group in the molecule is mixed together, and then (c) a polymer having an acetyl/acetyl group is added. It provides a method for manufacturing products.

It is not always clear whether a polymer with aceI/acetyl groups is used in combination with, for example, cuprous oxide, or why a certain amount of copper ions can be released, but the interaction between aceI/acedel groups and copper compounds is not clear. Formation of acetyl-1 bond, and further, regeneration of the acetyl group by promoting hydrolysis of the acetyl group in an alkaline aqueous solution, and an accompanying increase in the water solubility of the polymer. It is also 1(f-measured) that 1f is real or has some function 1 system.

The polymer having an acetyl-acetyl group used in the present invention can be prepared by polymerizing a monomer having an acetoacetyl group or by reacting a polymer having a hydroxyl group with diketene.

C1l.

ncll, ・-C- C-=0 '0 01
11 lIC1,, -CH2-
C1120-C-CIl□-C-CI+3113 Tortoise (cII,,-,-C)-:,: and-000 111N 0-CIl, CL-0-C-C112-,,,C-C1
1° (polymer with acetoacetyl group) 0-CI (
,, -CL-OH CL R 1 - - 壬(-CH12-C)(,CH2-CII)
÷□ C=0 0 01
II ll0-C112-C
112-0-C-C1l□-c-cl13 (polymer having an acetoacetyl group) A diketene polymer can be synthesized as a homopolymer or as a copolymer with a copolymerizable monomer. .

As is well known, the 0
0 0 '0111I II
lI C-Cl+2-C--C-CIl=C Ke1-type The homopolymerization of a monomer having an enol-type acetoacedel group is thought to be related to the tautomerism of enol mentioned above. However, as the polymerization rate increases, the polymer rapidly becomes gel-like, making it difficult to obtain a stable polymer unless a large amount of polymerization regulator is used.

Examples of monomers for forming the polymer having acel-acetyl groups used in the present invention include the following reaction products of unsaturated alcohols and diketenes.

2-Hydroxyethyl acrylate 1-, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate 1., 2-hydro-dipropyl methacrylate 1.
, polyethylene glycol monomethacrylate-I., allyl alcohol, and the like.

-grade alcohols react more easily with diketene,
For the present invention, it is "-minutes."

Polymers containing xyl groups can be produced by polymerization of monomers having hydroxyl groups or copolymerization with other monomers, for example, saponified products of polyvinyl acetate or copolymers thereof, or acetals, polymers, and butyralized polymers thereof. There is.

The reaction between hydroxyl groups and diketene is carried out in a closed container at 60°C.
It is carried out at different temperatures and in the presence of a catalyst such as an organic tin compound or a tertiary amine.

Rosin is a typical example of a compound having one carboxyl group, and components that can be used similarly to rosin in the present invention include fatty acids, which are hydrolyzed components of natural fats and oils of C12 or higher, or terpenes and maleic anhydride. Monoesters of adducts, monoesters of petroleum resin and maleic anhydride adducts, monoesters of polybutadiene oligomer and maleic anhydride adducts, etc. an unsaturated hydrocarbon oligomer that can
A molecule having substantially one carboxyl group in one molecule, which is obtained by adding maleic anhydride and monoesterifying the acid anhydride group with a desired alcohol.3
000 or less oligomer.

The reason for specifying the molecular weight as 3000 is that the molecular weight that causes a limit to compatibility with the polymer is approximately around this range, and of course it depends on the structure, but increasing the molecular weight higher than this will require mixing the mixture with cuprous oxide into the polymer. This is also because when it is added, its stabilizing effect is impaired.

The most desirable molecular weight of the oligomer having one carboxyl group is 200 or more and 1,500 or less.

In the present invention, a polymer having an ace1-acedel group may be used alone, or a multicomponent copolymer may be used in combination with a water-soluble monomer containing or not containing a reactive functional group, or a water-insoluble monomer.

Is there any particular restriction on the monomers that copolymerize with monomers having acetyl/acetyl groups to form a polymer? For example, representative examples of hydrophobic monomers include sutyrene, hinyltoluene, and methyl methacrylate. Examples of hydrophilic monomers include hinylpyrrolidone, acrylamide, acrylic acid, methacrylic acid, maleic anhydride, maleic acid monoesters, fumaric acid monoesters, itaconic acid, 2-hydroxyethyl acrylate-1,
Examples include 2-human 1-fuxyedyl methacrylate-1, 2-hydroxypropyl acrylate-32-hydroxypropyl methacrylate-1-1, and allyl alcohol.

Acryloni-1-hesyl is treated as hydrophobic since the polymer is not water soluble.

Polymerization is carried out by existing methods. The inorganic copper compound used in the present invention is typically cuprous oxide, which is sufficient for the purpose of the present invention; other examples include copper powder, basic copper chloride,
Examples include basic sulfuric acid steel, copper carbonate, basic copper carbonate, basic silver phosphate, copper hydroxide, and silver silicate. The amount used is 10 to 200 parts per 100 parts of resin, and may be increased or decreased as necessary.

The present invention does not preclude the use of known antifouling agents, such as dithiocarbamic acid, in addition to the copper compound described above.

The antifouling paint composition of the present invention comprises (a) an inorganic copperide and/or copper (b) a resin J having 1.3000 or less molecules and one carboxyl group in the molecule, or a fatty acid; c)
It is fine if it is obtained by using a polymer containing an acetylene group or used immediately after production, but if it is used after a period of time, there is a problem of kelization.

That is, if rosin is added to a polymer with reactive functional groups and then cuprous oxide is added to the system, premature gelation may occur.

1. However, as described above, if the rosin and cuprous oxide are kneaded in advance to a thickened state, gelation is unlikely to occur even when this mixed system is added to a polymer having a reactive functional group.

In reality, rosin is in a form dissolved in a solvent, and the same is true for polymers, but this is sufficient for practical purposes.

It goes without saying that the antifouling paint composition of the present invention may contain colorants, fillers, and bath agents, if necessary.

〔Example〕

Examples are provided below to aid in understanding the invention.

1. In a 1P separable flask equipped with a stirrer, reflux condenser, thermometer, and gas inlet tube, add 2-acetoacedelethyl methacrylate-1-3002. , 57 g of isofidyl methacrylate, 1.4 g of acrylic acid, 3 g of 1゜butyl lauryl mer-butane, 3 g of ASOJIS 2 soph diron, 3 g of ethyl acetate, and polymerized for 12 hours at a temperature of 65 to 70°C in a nitrogen stream. did.

During this period, administer 1 dose each of azobisisophthyronitrile every 4 hours.
Two portions of 5 d each were added.

Pale yellow multi-component copolymer (A) with a polymerization rate of about 95%
was gotten. The number average molecular weight was 68,000.

WW grade wood rosin (molecular weight 340-350) made from rosin and flax
Dissolve 0s in toluene 3003, add cuprous oxide 220 to this
0g in a closed mixer to form a paste-like kneaded product (
B).

This kneaded product (B) was stable and maintained a fluid state as long as it was stored in a closed container.

Mix 135 parts of the kneaded material (B) and 15 parts of toluene to 100 parts (by weight) of the polymer (A) to obtain a mixed paint (b). This mixed paint was stable and paintable for over a week.

On the other hand, on the other hand, a system in which 1.00 parts of polymer (c), 60 parts of a toluene solution of rosin (50%) and 150 parts of cuprous oxide were mixed turned into a gel about 10 minutes after mixing.

A mixed paint of polymer (A,) and kneaded product (Bl) was applied onto a Honply I-steel plate whose back side was anti-corrosion coated with epoxy resin, so that the dry coating thickness was approximately 70 to 100μ.
r) was painted and dried.

Pencil hardness 2H to 3T-1, diagonal adhesion test],
A coating of OO/100 was obtained.

Copper ion elution test The above painted sample was tested by Rechem (Rech).
Leaching test 1 for elution of copper ions was carried out according to the method using chrysin solution (um).

That is, chrysin 1.785g salt
27.960y0.1% caustic sorter 28.
8 cc distilled water 1.000 cc
Use a solution whose pH has been adjusted to 10.5.

The acceleration magnification is usually said to be 20-30 times, but here we calculated it as 20 times.

The elution amount of copper ions during the first 3 days (equivalent to 60 days) of the start of the test was 1-03 μg7 cm2/day to 84 μy/c on average.
It was somewhat inconsistent with m2/day, or 43, equivalent to 360 days.
μg7 cm27th, after that 760 mouths equivalent 37μy/
It became almost constant at cm'/day.

Install the stirrer, reflux condenser, waste inlet tube, and thermometer.
In a separate flask, add 200 g of 2-acetylacetyl ethyl acrylate and 60 g of 2-vinylpyridine.
2y, 42g of styrene, MIM ethyl 2969, l-
Add 3 g of phthyl lauryl mercabutane and 3 g of asohis isophthylonyl-l-lyl, and heat at 70 to 75°C in a nitrogen stream.
Polymerization was carried out for ζ12 hours.

During the course of the reaction, 5 y of Asohisophiduronitrile was added twice every 4 hours.

A polymer with a polymerization rate of 96% and a number average molecular weight of 69,000 was obtained.

To this copolymer, 76 g of benzyl chloride was added to convert hensylpyridinium chloride type 45th-class ammonium chloride. A copolymer (B) having a light yellowish brown color and a viscosity of about 60 voices was obtained.

Preparation of kneaded product (n) of cuprous oxide and 1--2 oil fatty acid.
150 parts of Harima Kasei Co., Ltd. (molecular weight: 300) were dissolved in 150 g of 1 to 1 kg, and cuprous oxide 10009 was stirred with a mixer to produce a base-like kneaded product (IT).

This kneading! 1 (b) was stable for more than a week in a sealed container at room temperature.

100 g of polymer (B) was mixed with 130 g of kneaded product (II) which was left to stand for one week after kneading.The kneaded system could be coated without gelation even if it was left to stand for one week or more.

However, the system in which 80 g of cuprous oxide was mixed with 100 y of polymer (B) became thicker after 3B and became difficult to coat.

Separately, a system obtained by adding 15 g of 1-1-1-1-1-1-1-1-1-1-2-1-1-1-1-1-1-1-1-1-1-2-1-2-1-2-1-2-1-2-1-3 fatty acids and then kneading the mixture was the result of almost the same condition as the system in which 80 g of cuprous oxide was added and then kneaded.

Polymer (B) 100g, kneaded product (IT) 1.30y,
1.6 Add 20y of luene to make a homogeneous solution, and apply it twice to a final film thickness of 70μ on Punchirai 1~ steel plate.
Dry.

The back side is made by Showa Kobunshi Co., Ltd. to prevent rust.
Spraytum C-200''' was applied to a thickness of about 2+ nm, and accelerated test 1 was performed in the same manner as in Example 1.

Elution amount at the start of the test] 1/1μg/cm2/day, 6
The elution amount after 00 days was 3 μg/C1l+2/day, which was a sufficient antifouling amount.

``Yuushi Shigeto Polymer (cc!') A Styrene 4] 1.2-H 208 g of 1-oxyethyl methacrylate, 15 g of 1-phydyllauryl mercabutane, 2.5 g of azohisisophthyloni, 25 g of ethyl acetate
0 g was added, and polymerization was carried out at 70 to 75° C. for 16 hours in a nitrogen stream.

During this period, take 1 dose of Asohisofujironi every 4 hours twice.
Added 15g of Heril.

The polymerization rate is approximately 96%, and the number average molecular weight is 70,000.

Lower the temperature to 60℃.
In addition, diketene 9CNt was added dropwise for about 1 hour. After finishing dropping, keep at 60°C for 6 hours.

As a result of infrared analysis, it was estimated that about 70% of the hydroxyl groups were acetoacetylated.

The obtained polymer contained approximately 50 mol% of 2-acetyl-acetyl ethyl methacrylate-I, 20 mol% of styrene, and 2-acetyl ethyl methacrylate-I.
Hydroxyethyl methacrylate-1 corresponds to about 30 mol % of a multicomponent copolymer 7).

A pale yellowish brown, sill-like copolymer (c) was obtained.

Production of kneaded product (lI) 100 parts of monomethyl ester of α-terpinene-maleic anhydride adduct (50% solution of methane), 50 parts of cuprous oxide, 50 parts of basic copper carbonate, and 50 parts of copper powder. The mixture was kneaded to produce a paste-like kneaded product (III).

This kneaded material (IT) is kept in a sealed state for at least 1 week.
It was bistable and showed no tendency toward Kelization.

100 parts of kneaded material (Tll) to 100 parts of polymer (c),
720 parts of Methyl Ethyl Ke I was mixed, and in the same manner as in Example 2, approximately 70 tons was coated to a thickness and dried.

The mixed system of polymer (c) and kneaded product (b) slightly thickened, but did not gel, and remained stable for more than one month.

Separately, a system in which 100 parts of polymer (c), 50 parts of cuprous oxide, 50 parts of basic carbonated steel, and 50 parts of copper powder were mixed turned into a kelp state after being left overnight.

In the coating film copper ion elution test I, the initial test value was 113 μ7.
/ cm2/day, equivalent to 480 days, is 27
It was μy/ctn2/day.

1st prize for “Fire Niro”.

30cm x 30cm
After coating and curing to a thickness of +nm, Example 2.3
The mixture system of each polymer and kneaded product manufactured by
After drying, it was left in the sea at a depth of 1 m at low tide from April to October, and tests were carried out. As a comparative example, unpainted Slay 1~
A board was used.

At the end of the test, the unpainted slate board had shells,
The surface of the pot was completely covered with seaweed and seaweed, but it was coated with a mixture of the polymer of the present invention, a mixture of an oligomer containing a carboxyl group, and an inorganic copper compound. All of the boards tested had 14 seaweed-like f values, but no shellfish was observed.

〔Effect of the invention〕

Since the antifouling paint composition of the present invention is configured as described above,
It has a long gelation time and has excellent paintability on substrates, and when immersed in seawater, the elution rate of copper ions can be controlled by controlling the concentration of specific functional groups, so it has excellent stain resistance for a long time. It is possible to show the coating film performance.

2,

Claims (1)

[Scope of Claims] 1. (a) an inorganic copperide and/or copper, (b) a resin or fatty acid having a molecular weight of 3000 or less and having one carboxyl group in the molecule, and (c) a polymer having an acetoacetyl group. An antifouling paint composition comprising the combination of . 2. (a) inorganic copperbide and/or copper, and (b)
A method for producing an antifouling paint composition, characterized in that a resin or fatty acid having a molecular weight of 3000 or less and having one carboxyl group in the molecule is mixed in advance, and then (c) a polymer having an acetoacetyl group is added. .