JPH11115113A - Antifouling laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve persistence and handleability of an antifouling effect by covering at least one side surface of a base material with a self-abrasion type antifouling resin film. SOLUTION: At least one side surface of a base material made of a fiber cloth is covered with a self-abrasion type antifouling resin film. The film contains a hydrolyzable resin and an antifouling agent. As the hydrolyzable resin, a resin of the type having a group for generating a hydrophilic group by a hydrolysis at a side chain of the resin and dissolving at the time of effecting a suitable hydrolysis in sea water such as, for example, a metal acrylic resin having a metal ester due to hydrolyzable copper, zinc or the like at an end of a side chain is used. As the agent, a copper, silver, zinc, tin, nickel or the like is used as an inorganic antifouling agent, and as an oxide, sulfide or alloy of each of these metals, a cuprous oxide, rhodan copper, copper-nickel alloy or the like is used. Thus, effects of algae prevention and shellproofness can be kept for a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an antifouling laminate having an antifouling property.

[0002]

2. Description of the Related Art When a large amount of aquatic fouling organisms such as barnacles, mussels and blue seas adhere to marine structures,
Significant industrial disadvantages arise. For example, if it adheres to a ship, fuel is wasted more than necessary due to an increase in frictional force during navigation.If it adheres to a fixed net or aquaculture nets, the net itself sinks due to an increase in weight, and a great deal of labor is required when lifting. Is required. Adhesion to the power plant intake pipes has also been a major obstacle. In order to solve these problems, a method of applying an antifouling paint containing an organotin compound to a ship, a fishing net, or a cloth has been widely used.

[0003] In recent years, however, accumulation of organotin compounds in fish and shellfish has been pointed out worldwide, and there has been an increasing expectation for an effective system for preventing fouling organisms from attaching to organotin compounds. The fact is that it has not been developed. Recently, attention has again been paid to copper-based compounds, which are considered to have a relatively smaller effect on fish and shellfish than organotin compounds.

However, when an antifouling paint is applied to a sheet-like marine structure such as an prevention film, there is a problem different from the case where the antifouling paint is applied to a rigid marine structure such as a ship or an intake pipe of a power plant. In other words, it is soft because it is a thin film, and only by applying an antifouling paint consisting of a conventional copper-based compound and a binder resin, which has been widely used for ship bottom paint, the resin is easily detached because there is no followability of the paint, There were problems such as being hard and difficult to handle.

[0005] In the antifouling effect, when the above antifouling paint is used, the antifouling effect depends only on the antifouling agent eluted from the coating film, and the elution speed is determined by the concentration gradient. Since it is based on the phenomenon, there has been a problem that a long-term stable antifouling effect cannot be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and has excellent durability of the antifouling effect.
Another object of the present invention is to provide an antifouling structure having excellent antifouling properties and excellent handling properties.

[0007]

The present invention employs the following means in order to solve such problems.

[0008] "An antifouling laminate characterized in that at least one surface of a substrate is coated with a self-polishing antifouling resin film." The aforementioned antifouling laminate containing a soiling agent. ”“ The self-polishing antifouling resin film has a rate of reduction of the film in seawater within a range of 0.1 μm / month to 20 μm / month. The said antifouling laminate. "" The antifouling laminate according to claim 2 or 3, wherein the antifouling agent is contained in the resin film in an amount of 0.01 to 80% by weight in solid content. " The antifouling laminate according to any one of the above, wherein the antifouling agent is at least one selected from inorganic copper compounds. ”“ The antifouling agent is selected from organic nitrogen sulfur compounds and organic halogen compounds. And at least one of the antifouling laminates described above. " , 20 inorganic copper compounds
At least one selected from an organic nitrogen-sulfur compound and an organic halogen compound is 1 to 10% by weight.
The antifouling laminate according to any one of the above, which is used in combination. "The antifouling laminate according to any one of the above, wherein the base material is a fiber cloth.""The antifouling laminate according to the above, wherein the fiber fabric has a strength of 300 kgf / 3 cm or more." The antifouling laminate according to any one of claims 1 to 9, having a softness by a measuring method of 3000 mgf or less. ".

[0009]

Embodiments of the present invention will be described below.

As the substrate used in the present invention, a fiber material and a fiber cloth are preferably used because the effects of the present invention are remarkably exhibited.

In the self-polishing type antifouling coating, the self-polishing type has a property of reducing the thickness of the film in water, and a film composed of an antifouling agent and a resin is preferably used.

The antifouling agent in the present invention is not particularly limited as long as it is a compound having an antifouling property. Examples of inorganic antifouling agents include copper, silver, zinc, tin and nickel.
Further, as oxides, sulfides, and alloys of these metals, cuprous oxide, rodan copper, copper nickel alloy, and the like can be used. Also, as an organic antifouling agent, copper dimethyldithiocarbamate,
Zinc dimethyldithiocarbamate, 2-n-octyl-
4-isothiazolin-33-one, N- (2 ', 6',
-Diethylphenyl) 2,3-dichloromaleimide, 4
-Chlorophenyl-3-iodopropargyl formal,
Diiodomethyl-p-trisulfone, 2-methylthio-
4-tert-butylamino-6-cyclopropylamino-s
-Triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea,
4,5-dichloro-2-n-octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N
-Fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt, 2-pyridinethiol-1-oxide copper salt, tetramethylthiuram disulfide, 2,3,5,6-tetrachloro-4- (methyl Sulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, pyridine-
Triphenylborane, 2,4-thiazolylbenzimidazole, manganese ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride and the like can be used. These compounds may be used alone or in combination.

The self-polishing type antifouling resin film of the present invention has an elution rate at 25 ° C. in seawater of 0.1 μm / month to 20 μm.
Preferably, it is in the range of m / month. If it is less than 0.1 μm / month, the dissolution of the antifouling agent is delayed, and the anti-biofouling property is poor. On the other hand, if it exceeds 20 μm / month, the coating film is severely consumed and the effect is lost quickly.

As a resin constituting such a self-polishing type antifouling film, a hydrolysis type resin is preferably used. As the hydrolysis-type resin, a resin having a group capable of forming a hydrophilic group by hydrolysis in a side chain portion of the resin, and being appropriately hydrolyzed and eluted in seawater is preferably used. A metal acrylic resin having a metal ester portion such as hydrolyzable copper or zinc at the terminal of the side chain can be used. The use of a soluble silicon polymer resin (soluble water glass) as another hydrolysis type resin is also effective. As such a hydrolysis-type resin, 0.1 to 20 μm at 25 ° C. in seawater.
Those which dissolve at a rate of / month are preferably used.

Further, the hydrolysis type resin has a glass transition point of-
It is desirable that the temperature be in the range of 20C to 100C. -20
If the temperature is lower than 100 ° C., the coating becomes sticky, and if the temperature is higher than 100 ° C., the coating is hard and unsuitable for use as an anti-pollution film requiring flexibility. In order to obtain more appropriate flexibility, the glass transition point is desirably in the range of −10 ° C. to 80 ° C., and more preferably in the range of −10 ° C. to 20 ° C.

The ratio of the hydrolyzable resin to the antifouling agent is such that the antifouling agent is contained in the resin film in a solid content of 0.01 to 80% by weight, more preferably 0.1 to 70% by weight. It is desirable. When an organic antifouling agent having a low specific gravity is used alone, an effect can be obtained with a content of about several%. However, when an inorganic antifouling agent having a high specific gravity is used alone, it is preferably 5%.
The content is 0 to 80% by weight, and more preferably 60 to 70% by weight.

In order to obtain an effect on a wider range of attached organisms, an inorganic copper compound is contained in the resin film as an antifouling agent in an amount of 20 to 70% by weight (to the film), an organic nitrogen sulfur compound, an organic nitrogen It is desirable to use at least one selected from halogen compounds in combination with 1 to 10% by weight (to the coating).

One of the means for obtaining flexibility is to add a plasticizer. The plasticizer is not particularly limited as long as it has compatibility with the resin, but diisodecyl phthalate, 2-ethylhexyl phenyl phosphate, tricresyl phosphate, dioctyl phthalate, chlorinated paraffin and the like are preferably used. . In particular, diisodecyl phthalate and 2-ethylhexyl phenyl phosphate are used in food packaging and medical applications, and are also desirable in terms of high safety.

Regarding the content of the plasticizer, the content of the
It is desirable to contain 1 to 10% by weight in terms of solid content. As a guide for softening, the addition of 5% by weight of a plasticizer as a solid content decreases the softness according to the Gurley-type softness measuring method to about half the value. It can be adjusted by adding.

The strength of the base fiber cloth is desirably 300 kgf / 3 cm or more.
Since the anti-pollution membrane is used continuously for a long period of several months to several years in the sea, it is required to withstand strong waves, tides, and collisions with obstacles in the sea. Is desired.

The condition for the softness of the antifouling laminate of the present invention is that the softness measured by the Gurley softness measuring method is 3%.
It is desirable that the amount be 000 mgf or less. 3000mgf
Above this, the ability to follow the base fabric is reduced, and the resin layer is likely to peel off. This can be appropriately adjusted by adding the above-mentioned plasticizer.

Sheet-like marine structures such as the pollutant laminate of the present invention for preventing biofouling, members that are required to be in contact with seawater for a long period of time and are required to prevent pollution, base fabrics for oil fences, floats for floats, etc. Can be used in general. In addition, many of the antifouling agents used are also effective against attached organisms in fresh water, and thus may be used for all underwater materials.

[0023]

The present invention will be described below in detail with reference to examples.

Example 1 Chemical formula (I)

Embedded image 100 parts of a solution of a hydrolyzable copper acrylic resin containing the structure of (a solid content 40%, Tg = 40)
C) and 64 parts of cuprous oxide were mixed and stirred well. This mixed resin was coated with a doctor knife on a polyester filament fabric having a plain weave structure with a basis weight of 330 g / m ^{2 so} that the solid adhesion amount on one side was 100 g / m ² . After drying this fabric at 160 ° C. for 3 minutes,
The backside was coated again under the same conditions and dried at 160 ° C. for 3 minutes to form a self-polishing antifouling coating having an adhesion amount of 200 g / m ^{2 on} both sides. Details are shown in Table 1.

[0025]

[Table 1]

Example 2 In the same formulation as in Example 1, cuprous oxide and N-
Example 2 was prepared by using (fluorodichloromethylthio) phthalimide in combination with 64 parts by weight and 7 parts by weight, respectively. The details are also shown in Table 1.

Examples 3 to 5 The same formulation as in Example 2 was used, except that N- (fluorodichloromethylthio) phthalimide was replaced with cuprous oxide and three kinds of organic antifouling agents to produce Examples 3 to 5. did. The details are also shown in Table 1.

Example 6 Example 6 was produced in the same manner as in Example 1, except that 5% by weight of diisodecyl phthalate was added as a plasticizer. The details are also shown in Table 1.

Examples 7 to 8 In the same manner as in Example 6, 5% by weight of 2-ethylhexylphenyl phosphate and tricresyl phosphate were added instead of diisodecyl phthalate, and Examples 7 to 8 were produced. The details are also shown in Table 1.

Example 9 Chemical formula (II)

Embedded image Using a hydrolyzable zinc acrylic resin having the following structure (solid content: 40%, Tg = 10 ° C.), Example 9 was produced in the same formulation as in Example 1. Details are shown in Table 1.

Example 10 Example 10 was produced using the same formulation as in Example 9 but using a zinc acrylic resin having a different Tg (solid content: 40%, Tg = 0 ° C.). Details are shown in Table 1.

Comparative Example 1 A conventional acrylic resin (Tg =
13 ° C.) to produce Comparative Example 1 with the same formulation as in Example 1. Details are shown in Table 1.

Comparative Example 2 An ordinary acrylic resin was used in place of the hydrolysis type resin.
Comparative Example 2 was manufactured using the same formulation as in Example 2. Table 1 for details
Shown in

Comparative Examples 3 to 5 In place of the hydrolysis type resin, a normal acrylic resin was used.
Comparative Examples 3 to 5 were manufactured using the same formulation as in Examples 3 to 5. Details are shown in Table 1.

Examples 1 to 8 and Comparative Examples 3 to 5 were evaluated for the softness, reduction rate of the coating film and antifouling property.

(Evaluation of rigidity) The rigidity was measured according to JIS L1.
It was measured by a 096 Gurley-type softness measurement method. Five samples were measured in each of the vertical and horizontal directions, and the average value was used.

(Evaluation of reduction rate of coating film) The reduction rate of the coating film was determined by cutting a sample into 5 cm square, immersing the sample in 250 ml of artificial seawater, and shaking with a constant temperature shaker (25 ° C, 20r).
pm), and after replacing the seawater once a day, the coating film was consumed for one month and then taken out and dried, and the reduction rate was determined from the difference between the film thickness of the dried product and the initial film thickness.

(Evaluation of Antifouling Property) The antifouling properties (algae-proofing and shell-proofing effects) of the laminates of the respective examples and comparative examples were evaluated by immersion tests in the sea in Owase Bay, Mie Prefecture. The submerged immersion test was evaluated over 24 months.

In the immersion method, the sample was mounted on a stainless steel frame having a square of 50 cm on a side and a diameter of 10 mm, suspended at a position of 1.5 m below the sea surface, and the state of biofouling was visually evaluated. The biofouling area (%) was evaluated. Table 2 shows the results.

[0040]

[Table 2]

From the results shown in Table 2, it was confirmed that the antifouling laminates of Examples 1 to 10 according to the present invention maintain excellent antifouling effects as compared with Comparative Examples.

[0042]

According to the present invention, the antifouling laminate obtained according to the present invention can maintain the effects of algae and shellfish for a long period of time.

Claims (10)

[Claims] 1. An antifouling laminate having a self-polishing antifouling resin film coated on at least one surface of a substrate. 2. The antifouling laminate according to claim 1, wherein the self-polishing resin film contains a hydrolyzable resin and an antifouling agent. 3. The antifouling laminate according to claim 2, wherein the self-polishing antifouling resin film has a decreasing rate of the film in seawater within a range of 0.1 μm / month to 20 μm / month. 4. The method according to claim 1, wherein the antifouling agent is contained in the resin film in a solid content of 0.1%.
The antifouling laminate according to claim 2, which is contained in an amount of from 0.01 to 80% by weight. 5. The antifouling laminate according to claim 2, wherein the antifouling agent is at least one selected from inorganic copper-based compounds. 6. The antifouling laminate according to claim 2, wherein the antifouling agent is at least one selected from organic nitrogen sulfur compounds and organic halogen compounds. 7. As the antifouling agent, 20 to 70% by weight of an inorganic copper-based compound, an organic nitrogen-sulfur-based compound,
At least one selected from organic halogen compounds,
The antifouling laminate according to claim 2, wherein 1 to 10% by weight is used in combination. 8. The antifouling laminate according to claim 1, wherein the base material is a fiber cloth. 9. The fiber fabric has a strength of 300 kgf / 3 cm.
The antifouling laminate according to claim 8, which is the above. 10. The method according to claim 1, wherein the bending resistance is 3 according to the Gurley bending resistance measurement method.
The antifouling laminate according to any one of claims 1 to 9, which has a weight of 000 mgf or less.