JPH021774A - Antifouling coating composition to be applied to wet surface - Google Patents

Abstract

PURPOSE:To obtain the subject composition easily applicable to a wet surface, continuing the antifouling effect over a long period and capable of forming a thick coating film in water by compounding copper (compound) powder to a composition containing a specific component such as epoxy resin and curable on wet surface. CONSTITUTION:The objective composition is produced by compounding (A) a composition curable on wet surface and containing (i) an epoxy resin (preferably having an epoxy equivalent of 140-1,000), (ii) a curing agent composed mainly of polyamide amine (preferably containing >=1.7 primary or secondary amino groups per one molecule on an average) and (iii) a silane coupling agent (e.g., gamma-glycidoxypropyltrimethoxysilane) with (B) preferably 10-60wt.% of copper (compound) powder (preferably spherical particle having an average particle diameter of <=100mum, flat particle having an average length of 10-1,000mum and an average thickness of 2-10mum or fibrous particle having an average diameter of 2-15mum and an average length of 10-1,000mum).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to an antifouling coating composition that can be coated in a thick film on wet surfaces, particularly underwater.

<Conventional technology> In recent years, underwater structures such as oil drilling or oil stockpile purging associated with offshore development, steel structures such as offshore plant ships, piers of huge bridges constructed on the ocean, and underwater steel structures of offshore airports have been developed. Building and construction of things continues to increase.

However, many of these devices are almost impossible to move from the installation area, and even ships must be pulled into a dry dock for maintenance, making maintenance work extremely complicated.

Marine deposits, such as Mt. Fuji pot, oysters, molluscs, and seaweed, can adhere to these steel structures and corrode them, increasing maintenance costs or rendering the structure itself unusable. Therefore, there is a need for an effective method to prevent marine deposits from adhering to and growing in underwater areas and splash zones.

Conventionally, antifouling paints containing antifouling agents such as organic tin have been used to prevent contamination and damage caused by marine deposits on such underwater structures.

However, these antifouling paints cannot be applied underwater, and in order to be applied, it is necessary to lift the underwater structure into the atmosphere (on land) and dry it.

In addition, the antifouling effect of the above antifouling paint does not last for more than a year, and it is usually lifted into the atmosphere once a year for maintenance to remove any marine deposits that may have adhered to it, and then reapplied after drying. It was necessary, the cost was enormous, and the work was extremely complicated.

<Problems to be Solved by the Invention> In view of the above circumstances, the present inventors have conducted extensive studies to develop a composition for applying to wet surfaces that has antifouling properties, and have found that:
A coating composition that exhibits excellent antifouling properties by blending copper or copper alloy powder with a specific composition using an epoxy resin as a base polymer, and can also be applied directly to underwater areas and splash zones. The present inventors have discovered that the following can be obtained, and have completed the present invention.

Means for Solving the Problems> That is, the present invention provides a wet surface curing composition containing an epoxy resin, a curing agent containing polyamide amine as a main component, and a silane coupling agent, in which powder of copper or copper alloy is added. The present invention provides an antifouling paint composition for use on wet surfaces, which contains the following:

Examples of the epoxy resin used in the present invention include epoxy resins conventionally used as paints for applying to wet surfaces.

Examples of such epoxy resins include substituted or unsubstituted glycidyl groups (e.g., glycidyl ether, glycidyl ester, glycidyl amine, glycidyl Examples include those having at least one imine (imine, etc.) in the molecule. Specific examples of such epoxy resins include diglycidyl ether of bisphenol, diglycidyl ether of bisphenol F, epoxy resin of phenol novolac, and glycidyl ether of alkylene oxide adducts of bisphenols.

There are no particular restrictions on the epoxy resin used in the above epoxy resin, but
Preferably, those having an epoxy equivalent of about 140 to 1000 are used. If the epoxy equivalent is too small, the properties of the resulting cured coating film will deteriorate, and if it is too large, the epoxy resin will tend to become solid and difficult to handle.

- It is preferable to use a compound having an average epoxy group of 1.5 or more in the molecule, and by using a compound having an average epoxy group of 1.5 or more, the properties of the cured coating film obtained can be improved. I can do it.

The epoxy resin used in the present invention is usually liquid or semi-solid, and solid epoxy resin is n-
Butyl glycidyl ether, acrylic glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, etc. can be mixed with a diluent capable of dissolving solid epoxy resin and used in a liquid or semi-solid form. .

The curing agent for the epoxy resin used in the present invention is mainly composed of polyamide amine, and preferably has an average of about 1.7 or more primary or secondary amino groups per molecule. used.

Specifically, polymerized fatty acids such as dimer acid and trimer acid obtained by polymerizing higher fatty acids having unsaturated bonds in the molecule such as liluic acid, oleic acid, linoleic acid, elaidic acid, and wasylic acid, and polyamines, especially fats. Examples include condensation reaction products with group polyamines.

As the polyamine, polyamines having two or more amino groups having at least one active hydrogen atom per molecule are used in view of condensation reactivity, such as aliphatic diamines that do not contain a ring structure in the molecule. , alkylene polyamines, branched polymethylene diamines, polyalkylene polyamines, and aliphatic diamines containing aromatic residues, aliphatic residues, or heterocyclic residues in their ring structure. Note that these polyamines may be used alone or in combination of two or more and subjected to the condensation reaction.

Among polyamide amines, those most typically used are condensates of dammer acid or trimer acid of liluic acid and various polyamines.

The above polyamide amine has an amine value of 100 to 100 to improve the properties of the cured coating film obtained with the composition of the present invention.
500, and the active hydrogen equivalent is preferably in the range of 50 to 150, and the amount of the curing agent is preferably set in the range of 0.5 to 2.5 equivalents per equivalent of the epoxy resin.

If the amount is less than 0.5 equivalents, curing may be insufficient, and if it exceeds 2.5 equivalents, unreacted curing agent may remain in the cured coating film, which may adversely affect the properties. .

In the present invention, the polyamide amine acts as a main component of the curing agent, but BF serves as a subcomponent.

Curing accelerators such as amine complexes, hexahydrophthalic anhydride, dicyandiamide, imidazoles (such as 2-ethyl-4methylimidazole), triethylenetetramine, and modified aliphatic or modified aromatic polyamines can also be blended as appropriate.

In addition, dibasic acids such as azelaic acid and fumaric acid and dibasic acids such as azelaic acid and fumaric acid
, 6-hexanedithiol, 1,8-octanedithiol, and other chain extenders and crosslinking agents such as dimercaptan, etc. 4,4'-dicyclopentylmethylene diisocyanate, etc.), aliphatic amines (ethylenediamine, etc.), aliphatic polyamines (diethylenepolyamine, etc.), alicyclic diamines (1,2-diaminocyclohexane, etc.), heterocyclic diamines (N(aminoalkyl)piperazine having 1 to 12 carbon atoms, etc.), aliphatic dihalides having 1 to 12 carbon atoms (such as 1,4-dibromobutane), dihydroxy aromatic compounds having 6 to 24 carbon atoms ( catechol, resorcinol, 3-hydroxybenzyl alcohol, 1,3-dihydroxynaphthalene, bisphenols), etc.

Furthermore, in order to impart water resistance and flexibility to the cured coating,
Various polyamine-based curing agents and liquid acrylonitrile
A butadiene copolymer or the like may also be blended in an amount within 50% of the total amount of the composition. Examples of such polyamine-based curing agents include those mentioned above, and liquid acrylonitrile-butadiene copolymers have an average of about 1.7 to 3, more preferably about 1.7 to 2, curing agents per molecule.
Those containing three primary or secondary amino groups are preferred, and those having the above-mentioned primary or secondary amino groups at least at both ends of the molecule are preferably used.

The silane coupling agent used in the present invention is a component for improving the adhesion of the paint film in water, and by incorporating this component, the coating composition of the present invention can be used in the coating composition before curing. Things will disappear. In addition, the silane coupling agent strengthens the bonding force between the epoxy resin and other compounded ingredients, as well as the bonding force due to interaction with the steel base material, improving the water resistance of the cured coating film and improving its anti-corrosion performance. becomes excellent.

As such a silane coupling agent, for example, R
'5i(OR)s is used. however,
In the formula, R' represents an organic functional group such as an amino group, mercapto group, vinyl group, or epoxy group, and OR represents a functional group such as an alkoxy group. Specifically, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylacetosilane, γ-methacryloxypropyltrimethoxysilane, T-methacryloxypropyltris(β-methoxyethoxy)silane,
-methoxyethoxysilane), β-(3゜4-epoxycyclohexyl)ethyltrimethoxysilane, T-glydoxypropyltrimethoxysilane, γ-glydoxypropylmethyljethoxysilane, N-β-(aminoethyl)-T -Aminopropyltrimethoxysilane, N-β
-(aminoethyl)-7-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane,
N-β-aminoethyl-T-aminopropyltrimethoxysilane, bis(trimethylsilano)amine, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltritoxysilane, γ-chloropropyltrimethoxysilane, etc. can be given. In particular, aminosilane-based, mercaptosilane-based, and epoxysilane-based silane coupling agents are preferred, and more specifically, γ-glydoxypropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ -Mercaptopropyltrimethoxysilane and the like.

In addition, the blending ratio of the silane coupling agent is 0.05 to 5% by weight of the total amount of the epoxy resin and curing agent, and
．． It is preferable to set it as 1 to 2 times %.

When the blending ratio of the silane coupling agent is less than 0.05% by weight, the effect of the silane coupling agent may not be sufficiently exhibited and the adhesion and anticorrosion properties may not be improved. Also, 5
A blending ratio exceeding % by weight is undesirable because it adversely affects the mechanical properties of the cured product.

The antifouling coating composition of the present invention is made by blending copper or copper alloy powder into a wet surface curing composition containing the above components, and exhibits an excellent antifouling effect. The powder shape may be any shape including scaly, dendritic (needle), crushed, etc., and preferably has an average particle size of 100 μm.
spherical particles with an average length of about 10 to 1000 μm and an average thickness of about 2 to 10 μm, and an average diameter of about 2 μm.
Fibrous particles having a diameter of ~15 μm and an average length of approximately 10 to 1000 μm are used.

The blending amount of these powders is in the range of 5 to 75% by weight, preferably 10 to 60% by weight, based on the total composition; if it is less than 5% by weight, the elution of copper ions is too small and the antifouling effect is poor. If it exceeds 75% by weight, the cohesive force of the composition decreases, making the formation of a coating unstable, and the mechanical strength tends to decrease, which is not preferable.

The antifouling paint composition for application to wet surfaces of the present invention is composed of the above-mentioned components, and has a consistency of 50 to 300, preferably 80 to 300, from the viewpoint of workability during construction and adhesion of the coating film. 2
It is desirable to adjust to a range of 00. If the consistency is too small, the composition of the present invention will become hard and difficult to spread, and if it is too large, it will become soft, and the pressure applied to the object will not be sufficiently transmitted to the adhesive interface during application, resulting in poor adhesive strength. The coating film may deteriorate or the uncured coating may peel off or wash out due to water flow or waves. The consistency referred to in the present invention refers to the depth at which a specified cone perpendicularly penetrates into a sample under standard conditions using a penetrometer based on JIS K2220 at 25°C. is defined as one unit.

The composition of the present invention includes adjustment of consistency and specific gravity, improvement of workability,
If necessary, various fillers may be blended in an amount of 300 parts by weight or less per 100 parts by weight of the epoxy resin for the purpose of improving the mechanical strength of the cured coating film, relieving stress, etc. Examples of such fillers include calcium carbonate, clay carbon black, titanium dioxide, barium sulfate, metal powder, glass powder, glass flakes, cement, and inorganic fibers, as well as other appropriate diluents, various solvents, and colorants. , antirust pigments, etc. can also be blended.

The antifouling paint composition for applying to wet surfaces of the present invention can be applied not only to seawater or fresh water, but also to wet areas such as bathrooms and kitchens, and can be applied not only to steel structures but also to surfaces such as concrete and wood. It can also be constructed in the same way.

<Effects of the Invention> As described above, the antifouling paint composition for applying to wet surfaces of the present invention uses a composition with a specific composition using an epoxy resin as a base polymer, and also contains copper or copper alloy powder as an antifouling agent. Therefore, it can be easily applied to wet surfaces, and the antifouling effect lasts for an extremely long period of time, making it extremely useful industrially.

<Example> Examples of the present invention will be shown below and explained in more detail.

In addition, the following parts mean parts by weight.

Example 1 100 parts of bisphenol A diglycidyl ether (epoxy equivalent 260), 100 parts of talc, 0.5 parts of T-glydokiprobyl trimethoxysilane, 15 parts of old Portland cement, and 1 part of colloidal silica were stirred in a mixing pot. The mixture was mixed at 50° C. to form an epoxy resin compound system.

On the other hand, polyamide amine (active amine hydrogen equivalent 90) 1
00 parts of titanium dioxide, 5 parts of titanium dioxide, 45 parts of talc, and 1 part of colloidal silica were mixed at 50° C. in a stirring mixing pot to prepare a curing agent combination system.

100 parts of the above epoxy resin compound, 35 parts of hardener compound, copper powder (average particle size 4 μm, thickness 0, 1 to 0.3
pm, average aspect ratio 30) were uniformly mixed using a stirring mixer to obtain an antifouling paint composition for application to wet surfaces of the present invention. The consistency of this composition was 280.

The obtained composition was applied to an area of 2 m above water, 2 m below, 4 m wide, and 5 m long over the splash zone, tidal zone, and seawater area of the steel sheet pile of a seawall that had been installed for 5 years.
5ISSa2・1/ by water sand jet method
The base was treated until the coating was coated with a coating of 3 to 5 mm thick by a wet hand method.

When observed one year after painting, no cracking, peeling, or rust was observed, and no marine organisms were attached to the paint film.

Example 2 100 parts of bisphenol A diglycidyl ether (epoxy equivalent: 190), 100 parts of talc, 20 parts of calcium carbonate, and 1 part of colloidal silica were mixed in a stirring mixing pot at 50°C to prepare an epoxy resin compounded system.

On the other hand, polyamide amine (active amine hydrogen equivalent 125)
100 parts of titanium dioxide, 5 parts of talc, 1 part of colloidal silica, and 1 part of N-β-(aminoethyl)-r-aminopropyltrimethoxysilane were stirred in a mixing pot at 50°C.
The mixture was mixed to form a curing agent compound system.

The antifouling paint composition of the present invention is prepared by uniformly mixing 100 parts of the above epoxy resin blend, 70 parts of the curing agent blend, and 150 parts of copper powder (average particle size: 8 μm, spherical) using a stirring mixer. (consistency 120) was obtained.

The resulting composition was applied in the same manner as in Example 1, and the coating film was observed one year after application. The results are shown in Table 1.

Example 3 100 parts of bisphenol F diglycidyl ether (epoxy equivalent: 175), 20 parts of calcium carbonate, and 1 part of colloidal silica were mixed at 50° C. in a stirring mixing pot to prepare an epoxy resin compound system.

On the other hand, polyamide amine (active amine hydrogen equivalent 125)
100 parts, titanium dioxide 5 parts, colloidal silica 1 part,
One part of γ-mercaptopropyltrimethoxysilane was mixed at 50° C. in a stirring mixing pot to prepare a curing agent combination system.

The antifouling paint composition for applying to wet surfaces of the present invention is prepared by uniformly mixing 100 parts of the above epoxy resin compounding system with 60 parts of the curing agent compounding system and 400 parts of copper powder (average particle size 8 μm, 1 spherical) using a stirring mixer. (consistency 70) was obtained.

The resulting composition was applied in the same manner as in Example 1, and the coating film was observed one year after application. The results are shown in Table 1.

Comparative Example I An antifouling paint composition (consistency 260) was obtained in the same manner as in Example 1 except that T-glycidoxypropyltrimethoxysilane was not blended.

Construction was carried out in the same manner as in Example 1, and the observation results of the coating film one year after construction are shown in Table 1.

Comparative Example 2 An epoxy modified product of diethylenetriamine (active hydrogen equivalent: 52) was used in place of the polyamide amine used in Example 1, and 15 parts of the curing agent blended system and copper were added to 100 parts of the epoxy resin blended system of Example 1. Powder (same as Example 1)
An antifouling paint composition (consistency 200) is prepared by uniformly mixing 10 parts of
I got it.

Construction was carried out in the same manner as in Example 1, and the observation results of the coating film one year after construction are shown in Table 1.

Comparative Example 3 An antifouling paint composition (consistency 37
0) was obtained.

Construction was carried out in the same manner as in Example 1, and the observation results of the coating film one year after construction are shown in Table 1.

No. table

Claims (1)

[Claims] (1) Antifouling for wet surface construction made by blending copper or copper alloy powder into a wet surface curing composition containing an epoxy resin, a curing agent mainly composed of polyamide amine, and a silane coupling agent. Paint composition.