JPH02227465A - Enzyme-containing resin composition and coating containing same - Google Patents

Abstract

PURPOSE:To provide a composition persistent in antifouling nature for a long period without causing marine pollution. thus suitable for antifouling coatings for marine constructions, etc., comprising as essential components, a film-forming polymer and an immobilized enzyme prepared by carrying an enzyme of organism origin on an organic resin to effect immobilization. CONSTITUTION:The objective composition comprising (A) an immobilized enzyme prepared by physically and/or chemically carrying an enzyme on a resin (e.g. polystyrene gel, polyacrylic gel) and (B) a film-forming polymer (e.g. lacquer-type vinyl resin. isocyanate curing-type resin). It is preferable that said immobilized enzyme be prepared by physically carrying the enzyme on a resin consisting of (a) hollow granular polymer or (b) granular polymer having porous structure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful enzyme-containing resin composition and a coating material containing the same.

More specifically, the present invention includes, as essential components, a so-called immobilized enzyme in the form of a biological enzyme supported and immobilized by a rational means in a resin, and a film-forming polymer. The present invention relates to a resin composition containing such a biologically derived enzyme, and particularly to a resin composition for an antifouling coating for underwater structures or structures, and a coating composition containing the same.

[Conventional technology]

Submerged objects that are used for a specific purpose are usually covered with a multilayer paint coating, which is used to prevent the inhabitation and growth of marine organisms such as algae and barnacles. The dog's coat is usually coated with antifouling paint.

By the way, such antifouling paints contain antifouling agents in the form of suboxide steel, which is itself a poisonous substance, and which gradually reacts with seawater to form water-soluble salts. The staining agent, in the form of water-soluble salts, is sequentially removed from the paint film.
It will be eluted.

To make the elution concentration of this type of antifouling agent uniform to a certain extent,
An example of a substance that can inhibit the growth or proliferation of marine organisms over a relatively long period of time is a specific copolymer of tributyltin oxy-Pt-side chain.

However, such copolymers, upon hydrolysis,
Triotyltin oxide, which causes marine pollution, is constantly released, and the impact on fish and shellfish is truly immeasurable and serious.

These nine fatal flaws in the growth of marine life,
Suboxide steel has recently been reconsidered as an antifouling agent in consideration of the effects of the use of growth-inhibiting substances, but considering it is a heavy metal, it has no effect on biological systems. I can't say that.

Although many organic antifouling agents have been developed,
In general, they are only relatively low-molecular organic compounds, and since they are actually simply blended with antifouling resins, long-term antifouling effects cannot be expected. There's no way.

[Problem to be solved by the invention]

In other words, from the viewpoint of sustainability of long-term use, public health, and impact on biological systems,
The reality is that it is still difficult to find an antifouling paint that is comprehensively satisfactory.

However, in view of the various deficiencies in the conventional techniques mentioned above, the inventors of the present invention have developed a method that does not cause any marine pollution and does not have any adverse effects on marine life. As a result of extensive research with the aim of providing a resin composition that can maintain antifouling properties or antifouling effects over a long period of time, we have found that specific immobilized enzymes as detailed below are essential ingredients. By using it as
Having determined that it is possible to obtain a companion product with satisfactory performance by eliminating all of the nine drawbacks mentioned above, the present invention has now been completed.

[Means to solve the problem]

That is, the present invention involves supporting and immobilizing a biological enzyme in an organic resin by rational means, a so-called immobilized enzyme, a film-forming polymer, and an enzyme-containing resin as all essential components. The present invention provides a composition and a coating material containing the resin composition.

In other words, the present invention uses an immobilized enzyme (A) in which the enzyme is physically and/or chemically supported on a resin as an essential component.
The present invention aims to provide an enzyme-containing resin composition containing a film-forming polymer (B) and a film-forming polymer (B), as well as a coating material containing the resin composition.

Here, first, the above-mentioned immobilized enzyme (A) is
A biologically active biologically active enzyme whose main component is protein is supported on an organic resin such as a synthetic resin by physical or chemical means, or an appropriate combination of these methods. The origin of such enzymes may be animals, plants, microorganisms, etc., and the types thereof include oxidoreductases, transferases, hydrolases, elimination enzymes, isomerases, synthetic enzymes, etc. Any one can be used if it is found to be effective. Preferably, hydrolytic enzymes can be used, and more preferably proteolytic enzymes can be used. Example 9 Hatrigsin and other enzymes include promelain, etc. These enzymes do not need to be highly purified, and various commercially available enzyme preparations can also be used. Its alternative is r protease M'
``Amano'', Protease A ``Amano'', 2, -RazeP
, papain W-40, Zoloreso, Protease P ``Amano'', Protease Sr7 Mano'' or No9 Ncreade 7F'' [All of the above are from Ohno Pharmaceutical Co., Ltd.! BB1
1 ma9 is "Protease B-500, Grote 7--k"
AZ, Maxam HP.

Is Alcalase actually 2, - Torase J [all of the above are from Denmark]? products made by e-Industries Co., Ltd.]. Also, these can be used alone or in combination.

Typical examples of resins to be supported include polystyrene glycol, I-reacrylglue, acrylic copolymers, I-lyester cocondensates, alkyd cocondensates, polyheptide cocondensates, and polymeric polysaccharides. Examples include organic resins such as natural or synthetic resins.

Furthermore, as a means for making the various organic resins listed above support the various enzymes listed above, the most representative physical method K is disclosed in Japanese Patent Application Laid-Open No. 61-62510. The enzyme or enzyme preparation is adsorbed onto the polystyrene glue particles as disclosed in the above publication, or the enzyme or enzyme preparation is adsorbed into the phosphor mixture at an early stage of *a. There is a method of immobilizing the polymer matrix in the coexistence of an enzyme or #* cleaving agent.

Next, we will exemplify some of the most representative chemical methods.

■ Periodic acid oxidation method An enzyme or an enzyme preparation having a sugar residue is reacted with periodic acid, thereby partially oxidizing the sugar residue to generate a carbonyl group, and then converting the carbonyl group into a - A method of reacting resins having an amino group with hydrogenated boronate and immobilizing them on resins, ■ Daltar aldehyde method. A method of immobilizing resins on resins by fully reacting with resins having a -grade amino group. (2) N-succinimidyl-3-(2-glydyldithio) f lobionate method. imidyl-3-(2-pyridyldithio)gloonate,
Method of immobilizing on resins by reacting with resins having a mercapto group (-8H) 1. Method of immobilizing calcium on resins by reacting with resins having a mercapto group (-8H). A method of immobilizing diimide on a resin by reacting it with a resin having a -class amino group, (2) monomethyl ether of polyethylene glycol supported on polyethylene glycol (one-end methoxylated polyethylene glycol), and 2.4. 6-
(1) reaction of the activated polyethylene glycol obtained in this way with an enzyme or an enzyme preparation), a method of supporting the enzyme or enzyme preparation on polyethylene glycol, and (1) an acid anhydride method. Another method involves reacting resins having an acid anhydride group to support them on resins.

In addition to these, for example, r CNBr-activated se7-y Cff-ase (S@phaross) 4
Bs) Resilu-activated Sepharose 4B or epoxy-activated Sepharose-Zero BJ (all of the above may be immobilized using a commercially available resin carrier such as a product manufactured by Pharmacia Co., Ltd.). The method is also an effective means.

When using the various chemical methods listed above, the characteristics of the enzyme or enzyme preparation, in particular, a safe reaction system that does not react with the functional groups involved in the specific activity of these enzymes etc. It goes without saying that you should choose and react accordingly.

On the other hand, the term "film-forming polymer (B)" refers to a polymer that is dried or cured to form a film by drying at room temperature, forced drying, and curing by baking. Any of the resins used as resins can be used without any particular problem.

Typical examples of the core film-forming polymer (B) include various types of resins such as lacquer-type vinyl resins, isocyanate-curing resins, non-aqueous dispersion-type resins, aqueous emulsion-type resins, and These resins are of various types, such as alkyd resins, alkyd-melamine resin combination systems, polyester-melamine resin combination systems, and acrylic-melamine resin combination systems.

The enzyme-containing resin composition of the present invention can be easily produced by simply mixing the two essential components, immobilized enzyme (A) and film-forming polymer (B), as listed above, using a conventional method. However, in addition to these two essential components, the composition of the present invention also contains additives that are usually blended into various organic resins that are the film-forming polymer (B). It goes without saying that other substances such as the like can be appropriately added as necessary.

Examples of such additives include heavy calcium carbonate, light calcium carbonate, carbon bed magnesium, precipitated barium sulfate, mica or titanium oxide, as well as cold water powder, powder, kaolin, clay, and calcined talc. ,
Silica sand, silica lime, ultrafine particulate silica, white karne,
Examples include inorganic pigments or fillers such as asbestos, dolomite powder, zinc white, or cargen black; or organic pigments such as azo, phthalocyanine, or quinacridone, and dispersed pigments thereof.

Please note that the composition of the present invention may be used in combination with a conventional antifouling agent if necessary, and the present invention does not in any way prevent such a combination. Leveling agents, various coupling agents such as titanium-based or silicone-based, anti-sagging agents, and diluting solvents are commonly used as additives.
Needless to say, it can be added as appropriate.

〔Effect of the invention〕

Since the enzyme-containing resin composition of the present invention uses nine enzymes that are supported and immobilized on organic resins by rational means, it does not cause marine pollution.
Moreover, it is useful because it maintains its antifouling properties for a long period of time.

Accordingly, the composition of the present invention can be applied in a wide range of fields, including as an antifouling paint for marine structures, as a biorepellent resin, and as a biorepellent paint.

〔Example〕

Next, the present invention will be explained in detail with reference to Reference Examples, Examples, Comparative Examples, Application Examples, and Comparative Application Examples. shall be.

Reference Example 1 [1liI cleavage example of immobilized enzyme (A)] According to the method disclosed in JP-A-61-62510, the particle size was 0.3 microns and the nonvolatile content was 45%. A copolymer emulsion containing polystyrene as the main component was obtained. In this example, PHt-7.0
I fixed it up.

Then, /ya/? is added to 100 parts of this copolymer emulsion. After mixing 5 parts of In (reagent grade 1), the mixture was kept in a constant temperature bath at 35° C. for 3 hours under stirring.

Afterwards, it was transferred to a freeze dryer and lyophilized to form a polystyrene resin that physically adsorbed Panoin, that is, an immobilized enzyme.

The particles in this book are white spherical particles, and according to the particle size measurement results using the Coulter Counter (Coult@r Countsr TA-...), they are secondary particles with a peak of 10 microns, that is, aggregates of primary particles. Just in case something is confirmed.

Hereinafter, this will be abbreviated as immobilized enzyme (A-1).

Reference Example 2 (same as above) Immobilized enzyme carrier rCNBr- manufactured by Pharmacia Co., Ltd.
By using 910 parts of activated Sepharose 4BJ, 90 parts of the enzyme "Protease A "Amano" and gold, and removing the
An immobilized enzyme with protease activity.

Next, this was washed with 6.8% phosphate buffer K to remove impurities, and then lyophilized into a dry powder.

This substance is an amorphous brown powder with a particle size of 40 microns.

Hereinafter, this will be abbreviated as immobilized enzyme (A-2).

Examples 1 and 2 and Comparative Examples 1 and 2 1st ff
According to the compounding composition ratio shown in K, all of the enzyme-containing resin composition of the present invention and the vinyl copolymer resin were blended with No4/#in and "Protease A "Amano" by a conventional method. A control enzyme-containing resin composition was obtained. (See item 1) Application examples 1 and 2. and Comparative Application Examples 1 and 2 The enzyme-containing resin compositions obtained in each Example and Comparative Example were separately diluted with toluene and Ford Cadem 4 for 30 seconds to prepare various antifouling products. Made with paint.

Next, each 1.5 m x 1.5 m nylon cultivation net was dip-coated with the above-mentioned antifouling paint.

Thereafter, the test fishing net was exploded by being left to dry at room temperature for 3 days.

Each fishing net was placed in the sea off the coast of Shirahama City, Wakayama Prefecture.
Immersion tests were conducted at a depth of m for 2 months, 4 months and 6 months.

The degree of adhesion of shellfish or seaweed at that time is expressed as an area ratio of adhesion occupancy in %, and the results are summarized in a transparent manner.

- "Acridic 56-425J... Dainippon Ink & Chemicals Co., Ltd. The glass transition temperature behind

Claims (1)

[Claims] 1. An immobilized enzyme (A) in which the enzyme is physically and/or chemically supported on a resin, and a film-forming polymer (B)
An enzyme-containing resin composition comprising: 2. The enzyme-containing resin composition according to claim 1, wherein the immobilized enzyme (A) is physically supported on a resin consisting of a hollow particulate polymer or a particulate polymer having a porous structure. 3. A paint comprising the enzyme-containing resin composition according to claim 1. 4. A paint comprising the enzyme-containing resin composition according to claim 2.